Substrate processing apparatus

ABSTRACT

The substrate processing apparatus is provided with a gas-liquid mixing nozzle for generating a process liquid mist by mixing a liquid and a pressurized gas, to discharge the process liquid mist to a substrate at high speeds. The liquid may be remover liquid, intermediate rinse liquid or deionized water. The reaction products which having been generated on the substrate in etching process is removed at high speeds with the flow of the mist, whereby the quality of the process is improved.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to an apparatus for removingresiduary pollution from various substrates such as a semiconductorwafer, a glass substrate for a liquid crystal display, a PDP (PlasmaDisplay Panel) substrate or a glass substrate and a ceramic substratefor magnetic discs.

[0003] 2. Description of the Background Art

[0004] In a substrate processing system, an apparatus for removingremaining contaminants from a substrate is used. Such remainingcontaminants may include reaction products generated on the substratedue to quality change of a resist. In most cases, the reaction productsare an organic substance. For example, when dry-etching is effected on athin film existing on the surface of the substrate with the use of aresist film as a mask, reaction products are generated on the substrate.This reaction products need to be removed efficiently. In the following,this circumstance will be explained more concretely.

[0005] Manufacturing processes of a semiconductor device include aprocess in which a metal thin film such as aluminum or copper formed ona substrate such as a semiconductor wafer is subjected to etching byusing a resist film as a mask to form wiring of semiconductor elements.

[0006] For example, as illustrated in FIG. 91A, electronic elements 8102are formed on a semiconductor substrate 8101, and a metal film 8103 isformed thereon. This metal film 8103 is made of, for example, aluminum.

[0007] Further, a resist film 8104 is formed on the metal film 8103.This resist film 8104 is formed through the following processes: resistis applied to a top surface of the metal film 8103 to be dried thereon,the dried resist is selectively exposed by an exposing device in theform of a wiring pattern, and a developing liquid is supplied to theexposed resist to remove unnecessary portions therefrom. In this manner,only the necessary portions of the metal film 8103 are masked by theresist film 8103, and in the succeeding etching process, the necessaryportions of the metal film 103 are allowed to remain without beingetched.

[0008] Next, a dry-etching process such as RIE (Reactive Ion Etching) iscarried out on the metal film 8103 masked by the resist film 8103 sothat portions of the metal film 8103 that have not been masked by theresist film 8103 are etched and removed and the portions remainingwithout having been etched are allowed to form metal wiring 8106.

[0009] When the dry-etching is carried out as described above, reactionproducts 8105, derived from the resist film 8103, etc., accumulate onthe sides of the metal wiring 8106, as shown in FIG. 91B.

[0010] In most cases, these reaction products 8105 are not removed inthe succeeding resist-removing process, and tend to remain on thesubstrate 8101 as shown in FIG. 91C, even after the removal of theresist film 8104.

[0011] When the substrate 8101 is sent to the next process withoutremoving such reaction products 8105, they tend to give adverse effectson the quality of the next process and thereafter; therefore, it isnecessary to remove them before the next process.

[0012] In order to remove the reaction products 8105, in theconventional substrate processing apparatus, a plurality of processliquids, such as a remover liquid, an intermediate rinse liquid anddeionized water, are successively supplied from respective nozzles whilethe substrate is being rotated. In the apparatus of this type, thefollowing improvements have been demanded.

[0013] (1) Improvements in the Throughput

[0014] Here, it has been known that, when the remover liquid anddeionized water are mixed, a phenomenon referred to as “pH shock” inwhich a strong alkali is generated, occurs, resulting in damages to themetal wiring.

[0015] For this reason, in the conventional method, in order not todirectly mix the remover liquid and deionized water, an intermediaterinse liquid is supplied so as to once remove the remover liquid fromthe substrate, and deionized water is then supplied to the substrate soas to carry out a deionized water cleaning process.

[0016] In such a conventional technique, the intermediate rinse steptakes a long time, resulting in adverse effects on the throughput.

[0017] Moreover, in the conventional technique, a large amount ofintermediate rinse liquid is required in the intermediate rinse step,resulting in high costs.

[0018] (2) Improvements in the Temperature Control in Process Liquids

[0019] Conventionally, with respect to the remover liquid used in theremoving process of these reaction products that have been generatedthrough dry-etching, those liquids adapted to a room temperature havebeen generally used. However, in recent years, remover liquids, whichexert an improved removing function on the removing products when usedat high temperatures, have been developed.

[0020] In the case when such a high-temperature type remover liquid isused, the remover liquid is heated to a temperature in the range ofapproximately 50 to 80 degrees in Celsius by using a temperature-raisingmechanism for the remover liquid, and the temperature of the removerliquid is controlled with high precision. In other words, when thetemperature of the remover liquid to be supplied to the substratevaries, it becomes impossible to carry out the removing process of thereaction products with high precision. For this reason, the temperaturecontrol of the remover liquid needs to be carried out so as to alwaysmaintain the temperature of the remover liquid to be supplied to thesubstrate at a fixed temperature.

[0021] However, in such a substrate processing apparatus, during anon-processing period of time up to the start of the process onsubstrates in the next lot after substrates in the preceding lot havebeen processed, or during a non-processing period of time up to thestart of the process on the next substrate after the process of apreceding substrate, the remover liquid tends to be cooled off insidepipes, etc., between the temperature-raising mechanism of the removerliquid and the remover liquid discharging section for discharging theremover liquid to the surface of the substrate, resulting in a failureto carry out the removing process of the reaction products with highprecision.

[0022] (3) Improvements in Nozzles

[0023] In the conventional substrate processing apparatus of this typefor removing the reaction products, the remover liquid is supplied to afixed portion on the substrate. For this reason, there is a differencein the process quality between the fixed portion and the other portions,failing to maintain the in-plane uniformity of the substrate.

[0024] In particular, the remover liquids have such a characteristicthat they exert the highest removing efficiency of the reaction productswhen used at the respective predetermined temperatures. For this reason,in the case when the remover liquid is supplied to the fixed portion ofthe substrate, it becomes difficult to maintain the in-plane uniformityof the substrate.

[0025] Further, the remover liquid supplying nozzle of such aconventional substrate processing apparatus is formed by a simplestraight tube that is directed toward the substrate with its tip beingopen. For this reason, since the remover liquid hits the substrate in adot form, it is difficult to maintain the in-plane uniformity in theprocess.

[0026] More specifically, the portion (referred to as a liquid arrivalportion) at which the remover liquid hits the substrate in the dot formmakes it possible to remove the reaction products in a comparativelyshort time, since a fresh remover liquid is always supplied thereto.However, the other portion (referred to as a liquid non-arrival portion)tends to have a slower process in comparison with the liquid arrivalportion. In other words, there are deviations in the time required forcompleting the process on the surface of the substrate.

[0027] For this reason, in the conventional substrate processingapparatus, it is necessary to wait for the completion of the process inthe liquid non-arrival portion in order to remove the reaction productsfrom the substrate. However, in contrast, the remover liquid slightlyhas a corrosion effect on the metal film 8103, with the result thatduring the waiting time for the completion of the process on the liquidnon-arrival portion, the corrosion might take place on the metal film8103 in the liquid arrival portion to a degree exceeding a permissiblerange.

[0028] Here, with respect to the substrate cleaning device, adroplet-injection cleaning method, which uses a cleaning double fluidsnozzle for strongly removing contaminants adhering the surface of thesubstrate, has been proposed.

[0029]FIG. 92 is a schematic drawing of a cleaning device in which theconventional cleaning double fluids nozzle is used. This cleaning deviceis provided with a cleaning cup 2051, a spin chuck 2052 for holding asubstrate W inside the cleaning cup 2051, an electric motor 2053 forrotating this spin chuck 2052, a gas supplying means 2055 for supplyingpressurized gas to the cleaning double fluids nozzle 2060 fordischarging droplets onto the surface of the substrate W, and a liquidsupplying means 2056 for supplying a pressurized liquid to the cleaningdouble fluids nozzle 2060. Moreover, a robot arm 2057 for holding andshifting the cleaning double fluids nozzle 2060 is installed.

[0030]FIG. 93 shows a cross-sectional view of the conventional cleaningdouble fluids nozzle 2060. The cleaning double fluids nozzle is providedwith a first tube path 2061 through which gas is transmitted, and asecond tube path 2062 the tip of which is allowed to penetrate the sidewall of the first tube path 2061 from the outside of the first tube path2061, and extended to the inside of the first tube path 2061 and throughwhich a fluid is transmitted. The tip of the second tube path 2062 isextended in the same direction as the direction in which the first tubepath 2061 is extended.

[0031] A substrate W is fixed to the spin chuck 2052, and rotated at apredetermined number of revolutions. Pressurized gas is supplied from agas supplying means 2055 to the cleaning double fluids nozzle 2060, anda pressurized liquid is supplied from a liquid supplying means 2056thereto, respectively. In the cleaning double fluids nozzle 2060, thegas and the liquid are mixed with each other so that the liquid ischanged to droplets in the form of mist. These droplets are acceleratedby the gas flow inside the first tube path 2061, and discharged from thetip of the first tube path 2061. The atomized droplets thus dischargedare made to collide with the surface of the substrate W, therebyremoving the contaminants adhering to the surface of the substrate W.

[0032] However, in the above-mentioned cleaning device, the gas and theliquid are mixed inside the cleaning double fluids nozzle 2060.Therefore, when the flow rate of one fluid is attempted to be changedindependently of the flow rate of the other fluid, the latter is alsochanged since the respective pressures interfere with each other insidethe first tube path 2061.

[0033] In other words, in the case when the gas flow rate is increasedso as to increase the cleaning strength, since the pressure of the gasinside the first tube path 2061 increases so that the flow rate of theliquid supplied from the second tube path 2062 is suppressed.Consequently, the droplets to be discharged from the tip opening of thenozzle of the double fluids nozzle 2060 tend to have cleaning strengthdifferent from the initial cleaning strength due to the suppressedliquid flow rate.

[0034] Consequently, fine particles such as dusts and slurries tend toremain on the surface of the substrate W, resulting in a serious problemof a reduced yield in the manufacturing process of the semiconductordevice.

[0035] Moreover, in the above-mentioned cleaning device, since the gasand the liquid are mixed inside the cleaning double fluids nozzle 2060,dusts are generated because irregularities on the inner wall of thenozzle 2060 are cut. The dusts may be also generated during the mixingoperation. The substances resulting from the dried liquid and adheringto the inside of the nozzle 2060 are taken off by the flow in thenozzle.

SUMMARY OF THE INVENTION

[0036] The present invention is directed to an apparatus for removingresiduary pollution from a substrate.

[0037] According to the present invention, the apparatus comprising: a)a spin mechanism for holding and rotating the substrate; and b) a liquidsupply mechanism for supplying at least one liquid onto the substratebeing rotated, comprising b-1) a mist supply mechanism for mixing a gaswith a processing liquid to generate mist and supplying the mist ontothe substrate being rotated in a removing process for removing theresiduary pollution from the substrate.

[0038] In an aspect of the present invention, the mist supply mechanismcomprising a mixing part having a mixing room for mixing gas with theprocessing liquid to generate the mist, and a nozzle having a taperedchannel for receiving the mist from the mixing room and supplying themist onto the substrate, the channel having a tapered part beingtapered-off toward a discharge end of the channel. The mist may beremover liquid, intermediate rinse for removing the remover liquid fromthe substrate being rotated, and/or deionized water.

[0039] In another aspect of the present invention, the mist supplymechanism comprising: a gas discharge mechanism for discharging the gasinto an open space on the substrate; and a processing liquid dischargemechanism for discharging the processing liquid into the gas in the openspace to generate the mist to be applied to the substrate.

[0040] In a preferred embodiment of the present invention, the mistsupply mechanism comprising: a processing liquid discharge mechanismhaving a first discharging outlet for discharging the processing liquidinto an open space; and a gas discharge mechanism having a seconddischarging outlet for discharging the gas into the processing liquid inthe open space just after the processing liquid is discharged from thefirst discharging outlet, to thereby convert the processing liquid intoliquid drops constituting the mist.

[0041] The present invention also provides an apparatus for removingresiduary pollution from a substrate, comprising: a) a spin mechanismfor holding and rotating the substrate; and b) a remover liquid supplyunit for supplying remover liquid onto the substrate being rotated toremove the residuary pollution from the substrate, c) a deionized watersupply unit for supplying a deionized water onto the substrate beingrotated, and d) at least one ultrasonic oscillator for applyingultrasonic wave to at least one of the remover liquid and the deionizedwater.

[0042] The residuary pollution may be caused in a dry-etching process inwhich a thin film formed on the substrate is removed through adry-etching step using a resist film as a mask. The origin of theresiduary pollution may be a resist used in an etching process of a thinfilm formed on the substrate. In a preferred embodiment of the presentinvention, the residuary pollution is an organic matter.

[0043] In another preferred embodiment of the present invention, anapparatus for removing residuary pollution caused in an dry-etchingprocess from a substrate, the apparatus comprising: a) a spin mechanismfor holding and rotating the substrate; and b) a remover liquid supplyunit for supplying remover liquid onto the substrate being rotated toremove the residuary pollution from the substrate while scanning thesubstrate with the remover liquid.

[0044] In a further another preferred embodiment of the presentinvention, provided is an apparatus for removing residuary pollutioncaused in an dry-etching process from a substrate, the apparatuscomprising: a) a spin mechanism for holding and rotating the substrate;and b) a remover liquid supply mechanism comprising: b-1) a pressuredgenerator for applying pressure to a remover liquid which is effectivefor removing the chemical residuary pollution to generate a pressuredremover liquid, and b-2) a nozzle for discharging the pressured removerliquid onto the substrate being rotated, and c) a deionized water supplymechanism for supplying deionized water onto the substrate beingrotated.

[0045] In a further another preferred embodiment of the presentinvention, provided is an apparatus for removing residuary pollutioncaused in an dry-etching process from a substrate, the apparatuscomprising: a) a remover liquid supply unit comprising a remover liquiddischarging unit for discharging remover liquid onto the substrate beingrotated to remove the residuary pollution from the substrate, b) atemperature controller for controlling a temperature of the removerliquid, c) a driver for moving the remover liquid discharging unitbetween a processing position from which the remover liquid isdischarged onto the substrate, and a stand-by position from which theremover liquid is discharged to a position defined out of the substrate,and d) a controller for controlling the driver and the remover liquiddischarging unit such that the remover liquid discharging unit islocated at the stand-by position and discharges the remover liquid tothe position defined out of the substrate, and the remover liquiddischarging unit is then moved to the processing position and dischargesthe remover liquid onto the substrate.

[0046] In a further another preferred embodiment of the presentinvention, provided is an apparatus for removing residuary pollutionfrom a substrate, comprising: a) a spin mechanism for holding androtating the substrate; b) a remover liquid supply unit for supplyingremover liquid onto the substrate being rotated to remove the residuarypollution from the substrate; c) a brush unit for brushing thesubstrate; d) a deionized water supply unit for supplying a deionizedwater onto the substrate being rotated; and d) a controller comprising afirst control procedure element for controlling the remover liquidsupply unit to supply the remover liquid onto the substrate beingrotated, a second control procedure element for controlling the brushunit to brush the substrate after the remover liquid is supplied ontothe substrate being rotated, a third control procedure element forcontrolling the deionized water supply unit to supply the deionizedwater onto the substrate being rotated after the substrate is brushed,and a fourth control procedure element for controlling the spinmechanism to rotate the substrate to disperse the deionized water fromthe substrate.

[0047] In another aspect of the present invention, an apparatus forremoving residuary pollution from a substrate, comprising: a) a spinmechanism for holding and rotating the substrate; and b) a processingliquid supply unit comprising a nozzle for discharging a spreadingcurrent of a processing liquid toward the substrate.

[0048] A cross section of the spreading current on the substrate may besubstantially an ellipse including a rotation center of the substrateand at least one point on a rotation circle defined by an edge of thesubstrate being rotated.

[0049] In another aspect of the present invention, an apparatus forremoving residuary pollution from a substrate, comprising: a) a spinmechanism for holding and rotating the substrate; b) a remover liquidsupply unit for supplying remover liquid onto the substrate beingrotated to remove the residuary pollution from the substrate, c) adeionized water supply unit for supplying a deionized water onto thesubstrate being rotated; and d) a controller comprising a first controlprocedure element for controlling the remover liquid supply unit tosupply the remover liquid onto the substrate being rotated, a secondcontrol procedure element for controlling the spin mechanism to rotatethe substrate to disperse the remover liquid from the substrate, and athird control procedure element for controlling the deionized watersupply unit to supply the deionized water onto the substrate beingrotated after the remover liquid is dispersed.

[0050] Accordingly, an object of the present invention is to uniformlycarry out the substrate processing.

[0051] Another object of the present invention is to improve thethroughput in the substrate processing.

[0052] Still another objective of the present invention is to properlycarry out the temperature management on process liquid.

[0053] The other objective of the present invention is to improve thestructure of a nozzle for discharging each process liquid.

[0054] These and other objects, features, aspects, and advantages of thepresent invention will becomes more apparent from the following detaileddescription of the present invention when taken in conjunction with theaccompanying drawings.

BRIEF DESCRIPTIONS OF THE DRAWINGS

[0055]FIG. 1 is a side view of a substrate processing apparatus 1001;

[0056]FIG. 2 is a top view of the substrate processing apparatus 1001;

[0057]FIG. 3 is a cross-sectional view of a gas-liquid mixing nozzle1027;

[0058]FIG. 4 is a flow chart that shows a substrate processing methodusing the substrate processing apparatus 1001;

[0059]FIG. 5 is a drawing that shows a hardware construction of thesubstrate processing apparatus 1001;

[0060]FIG. 6 is a drawing that shows a remover liquid supplying system1089, a deionized water supplying system 1091 and a nitrogen supplyingsystem 1093;

[0061]FIG. 7 is a detailed flow chart of the substrate processing methodusing the substrate processing apparatus 1001;

[0062]FIG. 8 is a top view of the substrate processing apparatus 1100;

[0063]FIG. 9 is a side view of a substrate processing apparatus 1100;

[0064]FIG. 10 is a flow chart that shows a substrate processing methodusing the substrate processing apparatus 1100;

[0065]FIG. 11 is a drawing that shows a solvent supplying system 1090and a nitrogen supplying system 1094;

[0066]FIG. 12 is a detailed flow chart that shows the substrateprocessing method using the substrate processing apparatus 1100;

[0067]FIG. 13 is a drawing that shows a schematic construction of asubstrate cleaning device in accordance with a first preferredembodiment of a second aspect;

[0068]FIG. 14 is a plan view of the substrate cleaning device inaccordance with the first preferred embodiment of the second aspect;

[0069]FIG. 15 is a longitudinal cross-sectional view that shows astructure of a cleaning nozzle in accordance with the first preferredembodiment of the second aspect;

[0070]FIG. 16 is a longitudinal cross-sectional view that shows astructure of a cleaning nozzle in accordance with a second preferredembodiment of the second aspect;

[0071]FIG. 17 is a side view of a substrate processing apparatusaccording to the first preferred embodiment of a third aspect;

[0072]FIG. 18 is a top view of the substrate processing apparatusaccording to the first preferred embodiment of the third aspect;

[0073]FIG. 19 is a piping drawing of the substrate processing apparatusaccording to the first preferred embodiment of the third aspect;

[0074]FIG. 20 is a hard configuration view of the substrate processingapparatus according to the first preferred embodiment of the thirdaspect;

[0075]FIG. 21 is a flow chart of the a substrate processing methodaccording to the first preferred embodiment of the third aspect;

[0076]FIG. 22 is a detailed view of the flow of the substrate processingmethod according to the first preferred embodiment of the third aspect;

[0077]FIG. 23 is a flow chart of the substrate processing methodaccording to the second preferred embodiment of the third aspect;

[0078]FIG. 24 is a side view of the substrate processing apparatusaccording to the second preferred embodiment of the third aspect;

[0079]FIG. 25 is a top view of the substrate processing according to thesecond preferred embodiment of the third aspect;

[0080]FIG. 26 is a piping drawing of the substrate processing apparatusaccording to the second preferred embodiment of the third aspect;

[0081]FIG. 27 is a hard configuration view of the substrate processingapparatus according to the second preferred embodiment of the thirdaspect;

[0082]FIG. 28 is a flow chart of the substrate processing methodaccording to the third preferred embodiment of the third aspect;

[0083]FIG. 29 is a detailed view of the flow the substrate processingmethod according to the third preferred embodiment of the third aspect;

[0084]FIG. 30 is a perspective view of the substrate processingapparatus according to the third preferred embodiment of the thirdaspect;

[0085]FIG. 31 is a top view of the substrate processing according to thethird preferred embodiment of the third aspect;

[0086]FIG. 32 is a cross section view with respect to F32-F32 of FIG.31;

[0087]FIG. 33 is a side view a substrate processing apparatus inaccordance with a first preferred embodiment of a fourth aspect;

[0088]FIG. 34 is a top view of the substrate processing apparatus inaccordance with the first preferred embodiment of the fourth aspect;

[0089]FIG. 35 is a drawing that shows piping of the substrate processingapparatus in accordance with the first preferred embodiment of thefourth aspect;

[0090]FIG. 36 is a drawing that shows a hardware construction of thesubstrate processing apparatus in accordance with the first preferredembodiment of the fourth aspect;

[0091]FIG. 37 is a flow chart that shows a substrate processing methodin accordance with the first preferred embodiment of the fourth aspect;

[0092]FIG. 38 is a detailed flow chart that shows a substrate processingmethod in accordance with the first preferred embodiment of the fourthaspect;

[0093]FIG. 39 is a flow chart that shows a substrate processing methodin accordance with a second preferred embodiment of the fourth aspect;

[0094]FIG. 40 is a top view of the substrate processing apparatus inaccordance with the second preferred embodiment of the fourth aspect;

[0095]FIG. 41 is a side view a substrate processing apparatus inaccordance with the second preferred embodiment of the fourth aspect;

[0096]FIG. 42 is a drawing that shows piping of the substrate processingapparatus in accordance with the second preferred embodiment of thefourth aspect;

[0097]FIG. 43 is a drawing that shows a hardware construction of thesubstrate processing apparatus in accordance with the second preferredembodiment of the fourth aspect;

[0098]FIG. 44 is a flow chart that shows a substrate processing methodin accordance with a third preferred embodiment of the fourth aspect;

[0099]FIG. 45 is a detailed flow chart that shows a substrate processingmethod in accordance with the third preferred embodiment of the fourthaspect;

[0100]FIG. 46 is a perspective view that shows a substrate processingapparatus in accordance with the third preferred embodiment of thefourth aspect;

[0101]FIG. 47 is a top view that shows the substrate processingapparatus in accordance with the third preferred embodiment of thefourth aspect;

[0102]FIG. 48 is a cross-sectional view taken along line F48-F48 of FIG.47;

[0103]FIG. 49 is a side view of a substrate processing apparatus 5001;

[0104]FIG. 50 is a top view of the substrate processing apparatus 5001;

[0105]FIG. 51 is a drawing that shows a remover liquid supplying system5089 and a deionized water supplying system 5091;

[0106]FIG. 52 is a drawing that shows a liquid pressurizing section5016;

[0107]FIG. 53 is a drawing that shows a hardware construction of thesubstrate processing apparatus 5001;

[0108]FIG. 54 is a flow chart that shows a substrate processing methodusing the substrate processing apparatus 5001;

[0109]FIG. 55 is a top view of the substrate processing apparatus 5100;

[0110]FIG. 56 is a side view of a substrate processing apparatus 5100;

[0111]FIG. 57 is a drawing that shows a solvent supplying system 5090;

[0112]FIG. 58 is a flow chart that shows a substrate processing methodusing the substrate processing apparatus 5100;

[0113]FIG. 59 is a schematic drawing that shows a substrate processingapparatus in accordance with a sixth aspect of the present invention;

[0114]FIG. 60 is a schematic side view that shows a construction of asubstrate processing section 6002 including a remover liquid storingvessel 6029, etc.;

[0115]FIG. 61 is a plan view that shows the construction of thesubstrate processing section 6002;

[0116]FIG. 62 is a block diagram that shows an essential electricalconstruction of the substrate processing apparatus;

[0117]FIG. 63 is a flow chart that shows a processing operation in thesubstrate processing apparatus at the time when a pre-dispensing processis executed;

[0118]FIG. 64 is a flow chart that shows a processing operation in thesubstrate processing apparatus at the time when an auto-dispensingprocess is executed;

[0119]FIG. 65 is a schematic plan view that shows a substrate processingapparatus in accordance with a first preferred embodiment of a seventhaspect;

[0120]FIG. 66 is a schematic side view that shows the substrateprocessing apparatus in accordance with the first preferred embodimentof the seventh aspect;

[0121]FIG. 67 is a schematic side view that shows the substrateprocessing apparatus in accordance with the first preferred embodimentof the seventh aspect;

[0122]FIG. 68 is a schematic side view that shows the substrateprocessing apparatus in accordance with the first preferred embodimentof the seventh aspect;

[0123]FIG. 69 is a block diagram that shows an essential electricalconstruction of the substrate processing apparatus;

[0124]FIG. 70 is a flow chart that shows a processing operation carriedout on a substrate W by the substrate processing apparatus in accordancewith the first preferred embodiment;

[0125]FIG. 71 is a flow chart that shows a processing operation carriedout on a substrate W by another preferred embodiment of the substrateprocessing apparatus in accordance with the first preferred embodiment;

[0126]FIG. 72 is a schematic side view that shows a substrate processingapparatus in accordance with a second preferred embodiment of theseventh aspect;

[0127]FIG. 73 is a flow chart that shows a processing operation carriedout on a substrate W by the substrate processing apparatus in accordancewith the second preferred embodiment;

[0128]FIG. 74 is a flow chart that shows a processing operation carriedout on a substrate W by another preferred embodiment of the substrateprocessing apparatus in accordance with the second preferred embodiment;

[0129]FIG. 75 is a side view of a substrate processing apparatus 8001;

[0130]FIGS. 76A and 76B are drawings explaining dispersing nozzle 8016;

[0131]FIGS. 77A and 77B are drawings explaining a dispersing nozzle 8016a;

[0132]FIG. 78 is a side view of a substrate processing apparatus inaccordance with a first preferred embodiment of a ninth aspect;

[0133]FIG. 79 is a top view of the substrate processing apparatus inaccordance with the first preferred embodiment of the ninth aspect;

[0134]FIG. 80 is a drawing that shows piping of the substrate processingapparatus in accordance with the first preferred embodiment of the ninthaspect;

[0135]FIG. 81 is a drawing that shows a hardware construction of thesubstrate processing apparatus in accordance with the first preferredembodiment of the ninth aspect;

[0136]FIG. 82 is a flow chart that shows a substrate processing methodin accordance with the first preferred embodiment of the ninth aspect;

[0137]FIG. 83 is a detailed flow chart that shows the substrateprocessing method in accordance with the first preferred embodiment ofthe ninth aspect;

[0138]FIG. 84 is a flow chart that shows a substrate processing methodin accordance with a second preferred embodiment of the ninth aspect;

[0139]FIG. 85 is a side view of a substrate processing apparatus inaccordance with the second preferred embodiment of the ninth aspect;

[0140]FIG. 86 is a top view of the substrate processing apparatus inaccordance with the second preferred embodiment of the ninth aspect;

[0141]FIG. 87 is a drawing that shows piping of the substrate processingapparatus in accordance with the second preferred embodiment of theninth aspect;

[0142]FIG. 88 is a drawing that shows a hardware construction of thesubstrate processing apparatus in accordance with the second preferredembodiment of the ninth aspect;

[0143]FIG. 89 is a flow chart that shows a substrate processing methodin accordance with the third preferred embodiment of the ninth aspect;

[0144]FIG. 90 is a detailed flow chart that shows the substrateprocessing method in accordance with the third preferred embodiment ofthe ninth aspect;

[0145]FIGS. 91A to 91C are drawings that explain a conventionaltechnique;

[0146]FIG. 92 is an explanatory drawing that shows a conventionalcleaning device; and

[0147]FIG. 93 is an explanatory drawing that shows a conventionalcleaning nozzle.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0148] <Definitions>

[0149] In the following preferred embodiments of the present invention,the “substrate” is a semiconductor substrate, and more specifically, asilicon substrate. Moreover, the substrate is provided with a thin filmformed on the top major surface of the substrate.

[0150] The “thin film” may be a metal film or an insulating film. Withrespect to metals forming the metal film, examples thereof includecopper, aluminum, titanium and tungsten. With respect to the insulatingfilm, examples thereof include a silicon oxide film and a siliconnitride film.

[0151] The “thin film” may include a film made of a mixture of metalssuch as copper, aluminum, titanium, tungsten and the like. Furthermore,the insulation film includes an organic insulation film and a lowdielectric interlayer insulation film. In this context, the term “thinfilm” includes not only the films in which the height dimension in thecross section of the direction perpendicular to the substrate on whichthe film is formed is shorter than the length of the bottom but also thefilms in which the height dimension is longer than the length of thebottom. Therefore, the thin film also includes those existing in theform of line or island when viewed toward the substrate, such as film orwiring which is locally formed on the substrate.

[0152] On the substrate that has been subjected to a dry-etching processfor the thin film by using a resist film as a mask, there are polymersthat are reaction products derived from the resist and the thin film inthe dry-etching process. The “substrate processing” is a process forremoving a residuary pollution which undesirably residues on a substrateand may include a polymer removing process for removing polymers fromthe substrate on which the polymers are generated.

[0153] The “remover liquid” is, for example, a polymer remover liquid.Examples of the polymer remover liquid include a liquid containing anorganic alkali liquid, a liquid containing an inorganic acid and aliquid containing an anmon-bifluoride-based substance. With respect tothe liquid containing an organic alkali liquid, DMF (dimethylformamide), DMSO (dimethyl sulfoxide) and hydroxylamine may be used.Moreover, with respect to the liquid containing an inorganic acid,hydrofluoric acid and phosphoric acid are listed.

[0154] Besides these, examples of the polymer remover liquid are liquidsof 1-methyl-2-pyrrolidone, tetrahydrothiophene 1,1-dioxide, isopropanolamine, monoethanolamine, 2-(2-aminoethoxy) ethanol, catechol,N-methylpyrrolidone, aromatic diol, tetrachloroethylene, and phenol,and, more specifically, a mixed solution of 1-methyl-2-pyrrolidone,tetrahydrothiophene 1,1-dioxide and isopropanol amine, a mixed solutionof dimethylsulfoxide and monoethanol amine, a mixed solution of2-(2-aminoethoxy)ethanol, hydroxylamine and catechol, a mixed solutionof 2-(2-aminoethoxy)ethanol and N-methylpyrrolidone, a mixed solution ofmonoethanol amine, water and aromatic diol, and a mixed solution oftetrachloroethylene and phenol.

[0155] Examples of the liquid containing organic amine (referred to asan organic amine series remover liquid) include a mixture ofmonoethanolamine, water and aromatic triol, a mixture of2-(2-aminoethoxy)ethanol, hydroxylamine and catechol, a mixture ofalkanolamine, water, dialkylsulfoxide, hydroxylamine, water,dialkylsulfoxide and an amine anticorrosive, a mixture of alkanolamine,glycol ether and water, a mixture of dimethylsulfoxide, hydroxylamine,triethylenetetramine, pyrocatechol and water, a mixture of water,hydroxylamine and pyrogallol, a mixture of 2-aminoethanol, ethers andsugar alcohols, and a mixture of 2-(2-aminoethoxy)ethanol,N-dimetylacetoacetoamide, water and triethanolamine. Furthermore, theliquid containing ammonium fluoride series substance (referred to as anammonium fluoride series remover liquid) includes a mixture of anorganic alkali, a sugar alcohol and water, a mixture of a fluorinatedcompound, an organic carboxylic acid and an acid amide solvent, amixture of alkyl amide, water and ammonium fluoride, a mixture ofdimethyl sulfoxide, 2-aminoethanol, an organic alkali aqueous liquid andan aromatic hydrocarbon, a mixture of dimethyl sulfoxide, ammoniumbifluoride and water, a mixture of ammonium bifluoride, triethanolamine,pentametyldiethylenetriamine, iminodiacetic acid and water, a mixture ofglycol, an alkyl sulfate, an organic salt, an organic acid and aninorganic salt, a mixture of an amide, an organic salt, an organic acidand an inorganic salt, and a mixture of an amide, an organic salt and aninorganic salt.

[0156] Furthermore, examples of the inorganic remover liquid containingan inorganic substance include a mixture of water and phosphoric acidderivative.

[0157] The “intermediate rinse liquid” is a liquid for removing theremover liquid from the substrate, and examples thereof include anorganic solvent such as isopropyl alcohol (IPA) or functional water suchas ozone water prepared by dissolving ozone in deionized water andhydrogen water prepared by dissolving hydrogen in deionized water.

[0158] When the ozone water in which ozone is dissolved in deionizedwater is used as the intermediate rinse liquid, it is possible to removethe reaction products and polymer resulting from quality change oforganic substance and resist more completely.

[0159] The remover liquid, intermediate rinse liquid and deionized waterare generally referred to as “process liquid” or “cleaning liquid”.

[0160] The “pH.shock” refers to a phenomenon in which upon contact of aremover liquid and deionized water, a strong alkali is generated, andsince the generation of such a strong alkali causes damages to a metalfilm, this needs to be reduced to a minimum.

[0161] (A. Preferred Embodiments According to First Aspect of thePresent Invention)

[0162] <I. Substrate Processing Apparatus 1001>

[0163]FIGS. 1 and 2 are drawings that show the construction of asubstrate processing apparatus 1001 according to a preferred embodimentof the present invention. Here, FIG. 1 is a cross-sectional view takenalong line F1-F1 of FIG. 2, and for convenience of explanation, hatchingis partially omitted from some portions.

[0164] As illustrated in FIG. 1, the substrate processing apparatus 1001is provided with a cup 1003 which has a virtually U-letter shape in itscross-section, and also has a virtually ring shape with an opening inthe center portion thereof as shown in FIG. 2, when viewed from above, aholding rotary section 1005 that is formed in a manner so as to stickout through the opening of the cup 1003 in the vertical direction asshown in FIG. 1 and that rotates while holding a substrate W, a removerliquid supplying section 1007 for supplying a remover liquid to thesubstrate W held by the holding rotary section 1005 and a deionizedwater supplying section 1009 for supplying deionized water to thesubstrate W held by the holding rotary section 1005.

[0165] The cup 1003 has a plurality of discharging outlets 1004 on thebottom thereof. Thus, an excessive portion of the liquid supplied to thesubstrate W drops along the inner wall of the cup 1003 to reach thedischarging outlets 1004, and is discharged out of the apparatus throughthe discharging outlets 1004.

[0166] The holding rotary section 1005 is provided with a spin motor1013 which is secured to an apparatus frame, not shown, and has adriving shaft placed in the vertical direction, a spin shaft 1014 thatis secured to the driving shaft of the spin motor 1013 and a vacuumchuck 1015 serving as a substrate holding member placed on the top ofthe spin shaft 1014.

[0167] The vacuum chuck 1015 has suction holes, formed in a suctionsurface that is an upper surface thereof, and air is sucked through thesuction holes. Thus, the substrate W, placed on the vacuum chuck 1015,is held by air suction applied through the suction holes. In thismanner, the vacuum chuck 1015 holds the substrate W by contacting onlythe back surface of the substrate W.

[0168] In this arrangement, the holding rotary section 1005 holds thesubstrate W placed on the vacuum chuck 1015 through suction applied bythe vacuum chuck 1015, and rotates the substrate W held on the vacuumchuck 1015 by driving the spin motor 1013.

[0169] The remover liquid supplying section 1007 is provided with afirst rotary motor 1017 which is secured to the apparatus frame, and hasa driving shaft placed in the vertical direction, a first rotary shaft1019 secured to the driving shaft of the first rotary motor 1017 and afirst arm 1021 connected to the top of the first rotary shaft 1019.

[0170] A remover liquid discharging nozzle 1011 is attached to the tipof the first arm 1021. The remover liquid discharging nozzle 1011 is atube-shaped member with its length direction set virtually in thevertical direction, and a remover liquid is supplied from one endthereof, with the other end supplying the remover liquid to thesubstrate W.

[0171] Moreover, a remover liquid spray nozzle 1012 is attached to thesame tip of the first arm 1021 through a bracket 1023 (indicated by analternate long and two short dashes line in FIG. 2). The remover liquidspray nozzle 1012, which sprays a remover liquid mist as will bedescribed later, is arranged so as to spray the remover liquid mist withan inclination of 45 degrees with respect to the surface of thesubstrate W. In other words, the remover liquid spray nozzle 1012 isinclined by 45 degrees with respect to the normal direction of the topmajor surface of the substrate W.

[0172] The above-mentioned remover liquid discharging nozzle 1011 andremover liquid spray nozzle 1012 are arranged so that the remover liquiddischarged from the remover liquid discharging nozzle 1011 and theremover liquid mist sprayed from the remover liquid spray nozzle 1012are allowed to intersect each other on the surface of the substrate W,and so that, when the remover liquid discharging nozzle 1011 and theremover liquid spray nozzle 1012 are allowed to pivot by the firstrotary motor 1017, the remover liquid discharged from the remover liquiddischarging nozzle 1011 and the remover liquid mist sprayed from theremover liquid spray nozzle 1012 are reciprocally shifted, asillustrated in FIG. 2, on a circular arc 1085 that passes through therotation center C of the substrate W and also intersects a rotationcircle 1095 that the end edge of the rotating substrate W forms at twopoints on the circumference thereof.

[0173] The deionized water supplying section 1009, which is secured tothe apparatus frame is provided with a second rotary motor 1031 having adriving shaft directed in the vertical direction, a second rotary shaft1033 secured to the driving shaft of the second rotary motor 1031 and asecond arm 1035 connected to the top of the second rotary shaft 1033.

[0174] A deionized water discharging nozzle 1024 is attached to the tipof the second arm 1035. The deionized water discharging nozzle 1024 is atube-shaped member with its length direction set virtually in thevertical direction, and deionized water is supplied from one endthereof, with the other end supplying the deionized water to thesubstrate W.

[0175] Moreover, a deionized water spray nozzle 1025 is attached to thesame tip of the second arm 1035 through a bracket 1026 (indicated by analternate two dots dash line in FIG. 2). The deionized water spraynozzle 1025, which sprays a deionized water mist as will be describedlater, is arranged so as to spray the deionized water mist with aninclination of 45 degrees with respect to the surface of the substrateW. In other words, the deionized water spray nozzle 1025 is inclined by45 degrees with respect to the normal direction of the top major surfaceof the substrate W.

[0176] The deionized water discharging nozzle 1024 and deionized waterspray nozzle 1025 are arranged so that the deionized water dischargedfrom the deionized water discharging nozzle 1024 and the deionized watermist sprayed from the deionized water spray nozzle 1025 are allowed tointersect each other on the surface of the substrate W, and so that,when the deionized water discharging nozzle 1024 and the deionized waterspray nozzle 1025 are allowed to pivot by the second rotary motor 1031,the deionized water discharged from the deionized water dischargingnozzle 1024 and the deionized water mist sprayed from the deionizedwater spray nozzle 1025 are reciprocally shifted, as illustrated in FIG.2, on a circular arc 1087 that passes through the rotation center C ofthe substrate W and also intersects a rotation circle 1095 that the endedge of the rotating substrate W forms at two points on thecircumference thereof.

[0177] <2. Gas-Liquid Mixing Nozzle>

[0178] The remover liquid spray nozzle 1012 and deionized water spraynozzle 1025 have the same structure, and a gas-liquid mixing nozzle 1027as illustrated in FIG. 3 is adopted as these nozzles.

[0179] The gas-liquid mixing nozzle 1027 is provided with acylinder-shaped mixing section 1030 forming a mixing chamber 1042 inwhich a gas and a liquid are mixed, a taper section or tapered channel1032 which has a tapered flowing path 1034 that has one end connected tothe mixing chamber 1042, and is narrowed toward the other end, and whichis connected to the mixing section 1030, and a straight flow section1037 which has a straight flowing path 1036 that has one end connectedto the tapered flowing path 1034, and continuously has a cross-sectionhaving the same shape toward the other end, and which is connected tothe above-mentioned tapered section 1032. Moreover, a gas introducingtube 1038 and a process liquid introducing tube 1029 are connected tothe mixing section 1030, and the mixing section 1030, the gasintroducing tube 1038 and the process liquid introducing tube 1029 arefixed by a housing 1028.

[0180] The mixing section 1030 is a member having a virtually cylindershape, through which a cylinder shape gas introducing tube 1038 havingan outer diameter smaller than the inner diameter of the mixing section1030 is inserted. More specifically, the mixing section 1030 and the gasintroducing tube 1038 respectively have cylinder shapes, with theircenter axes being coincident with each other. The end portions of thegas introducing tube 1038 are housed inside the mixing section 1030. Inother words, the mixing section 1030 is allowed to regulate aring-shaped space enclosing the end part of the gas introducing tube1038.

[0181] The taper section 1032 connected to the mixing section 1030 has acone shape. One end of the taper section 1032, connected to the mixingsection 1030, has an inner diameter that is the same dimension as theinner diameter of the portion of the mixing section 1030 to which it isconnected. The taper section 1032 has such a structure that the innerdiameter thereof is continuously narrowed from the one end toward theother end, and with this structure, the tapered flowing path 1034 thatis gradually narrowed inside the taper section 1032 is formed.

[0182] The straight flow section 1037, connected to the taper section1032, has a cylinder shape. One end of the straight flow section 1037,which is connected to the taper section 1032, has the same dimension asthe inner diameter of the portion of the taper section 1032 to which itis connected. Further, the inner diameter of the straight flow section1037 continuously has the same dimension from the above-mentioned oneend toward the other end. In other words, the straight flow section 1037has a flowing path whose cross-section continuously has the same shape(in this case, round shape) from one end to the other end, and thisflowing path whose cross-section continuously has the same shape forms astraight flowing path 1036.

[0183] These taper section 1032 and straight flow section 1037 areintegrally formed as one part.

[0184] In such a gas-liquid mixing nozzle 1027, a pressurized gas issupplied from the gas introducing tube 1038, and when a process liquidis supplied from the process liquid introducing tube 1029, the gas andthe process liquid are mixed inside the mixing chamber 1042 so that theprocess liquid forms a process liquid mist made of fine droplets. Then,the process liquid mist has its moving velocity accelerated through thetapered flowing path 1034 and the straight flowing path 1036, and theprocess liquid mist is finally sprayed from the tip of the straight flowsection 1037. In this case, the pressure of the gas supplied from thegas introducing tube 1038 is adjusted so that the velocity of theprocess liquid mist to be finally sprayed from the straight flow section1037 is accelerated to approximately sound velocity.

[0185] On the inner wall of the gas-liquid mixing nozzle 1027, particlesmight be generated due to failings from the inner wall since the gas andthe process liquid collide therewith at high speeds. However, since atleast the inner wall surface of the mixing chamber 1042, that is, thesurface of the inner wall surface of the mixing section 1030, is allowedto have a smooth surface so that the possibility of the particles isreduced. Here, the irregularities of the surface of the inner wallsurface of the mixing chamber 1042 are set to not more than 0.3 μm(preferably, not more than 0.1 μm) to form a smooth surface. Moreover,the mixing section 1030 is made from quartz and the taper section 1032and the straight flow section 1037 is made from fluoro-resin so that itis possible to reduce elusion of contaminants caused by the processliquids.

[0186] In the case when the gas-liquid mixing nozzle 1027 is adopted asthe remover liquid spray nozzle 1012, pressurized nitrogen gas issupplied to the gas introducing tube 1038 from a nitrogen supplyingsystem 1093, which will be described later, and a remover liquid issupplied to the process liquid introducing tube 1029 from a removerliquid supplying system 1089. Thus, a remover liquid mist is sprayedfrom the remover liquid spray nozzle 1012.

[0187] Moreover, in the case when the gas-liquid mixing nozzle 1027 isadopted as the deionized water spray nozzle 1025, pressurized nitrogengas is supplied to the gas introducing tube 1038 from the nitrogensupplying system 1093, and deionized water is supplied to the processliquid introducing tube 1029 from a deionized water supplying system1091. Thus, a deionized water mist is sprayed from the deionized waterspray nozzle 1025.

[0188] <3. Remover Liquid Supplying System, Deionized Water SupplyingSystem, Nitrogen Supplying System>

[0189]FIG. 6 shows the remover liquid supplying system 1089, thedeionized water supplying system 1091 and the nitrogen supplying system1093. The remover liquid supplying system 1089 is provided with aremover liquid pump 1047 for pumping the remover liquid from a removerliquid source 1045 outside the apparatus, a temperature-adjusting device1051 for adjusting the temperature of the remover liquid by heating orcooling the remover liquid pumped out by the remover liquid pump 1047 toa predetermined temperature, a filter 1049 for filtering contaminantsfrom the remover liquid that has been temperature-adjusted by thetemperature-adjusting device 1051, and a remover liquid nozzle valve1053 for opening and closing the flowing path of the filtered removerliquid to the remover liquid spray nozzle 1012.

[0190] This arrangement allows the remover liquid supplying system 1089to supply the remover liquid that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 1051 andpurified by the filter 1049 to the remover liquid spray nozzle 1012.

[0191] Moreover, the remover liquid supplying system 1089 also has aremover liquid discharging valve 1056 for opening and closing theflowing path of the remover liquid having been filtered to a removerliquid discharging nozzle 1011, and the discharging anddischarge-stopping operations of the remover liquid from the removerliquid discharging nozzle 1011 are controlled by opening and closing theremover liquid discharging valve 1056.

[0192] The deionized water supplying system 1091 is provided with adeionized water pump 1057 for pumping deionized water from a deionizedwater source 1055 outside the apparatus, a temperature-adjusting device1052 for adjusting the temperature of the deionized water by heating orcooling the deionized water pumped out by the deionized water pump 1057to a predetermined temperature, a filter 1059 for filtering contaminantsfrom the deionized water that has been temperature-adjusted by thetemperature-adjusting device 1052, and a deionized water spray valve1063 for opening and closing the flowing path of the filtered deionizedwater liquid to the deionized water spray nozzle 1025.

[0193] This arrangement allows the deionized water supplying system 1091to supply the deionized water that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 1052 andpurified by the filter 1059 to the deionized water spray nozzle 1025.

[0194] Moreover, the deionized water supplying system 1091 also has adeionized water discharging valve 1058 for opening and closing theflowing path of the deionized water having been filtered to a deionizedwater discharging nozzle 1024, and the discharging anddischarge-stopping operations of the deionized water from the deionizedwater discharging nozzle 1024 are controlled by opening and closing thedeionized water discharging valve 1058.

[0195] The nitrogen supplying system 1093 is provided with a nitrogensource 1067 for supplying pressurized nitrogen gas, a remover liquidside nitrogen valve 1066 for opening and closing the tube path from thenitrogen source 1067 to the remover liquid spray nozzle 1012, and adeionized water side nitrogen valve 1065 for opening and closing thetube path from the nitrogen source 1067 to the deionized water spraynozzle 1025. Thus, the supplying and supply-stopping operations ofnitrogen gas to the remover liquid spray nozzle 1012 are controlled byopening and closing the remover liquid side nitrogen valve 1066, and thesupplying and supply-stopping operations of nitrogen gas to thedeionized water spray nozzle 1025 are controlled by opening and closingthe deionized water side nitrogen valve 1065.

[0196] <4. Control Means>

[0197]FIG. 5 shows a control means 1069 of the substrate processingapparatus 1001.

[0198] To the control means 1069 are connected the spin motor 1013, thefirst rotary motor 1017, the second rotary motor 1031, the removerliquid pump 1047, the deionized water pump 1057, the remover liquidspray valve 1053, the deionized water spray valve 1063, the removerliquid discharging valve 1056, the deionized water discharging valve1058, the remover liquid side nitrogen valve 1066, the deionized waterside nitrogen valve 1065, the temperature-adjusting device 1051 and thetemperature-adjusting device 1061. As will be described in a substrateprocessing method, the control means 1069 controls these devicesconnected thereto.

[0199] In the present substrate processing apparatus 1001, thegas-liquid mixing nozzle 1027 is adopted as the remover liquid spraynozzle 1012 and the deionized water spray nozzle 1025. Since thegas-liquid mixing nozzle 1027 has a straight flow section 1037, it ispossible to regulate the remover liquid mist and the deionized watermist from dispersing. For this reason, the remover liquid mist and thedeionized water mist are accelerated to a predetermined velocity, andthe remover liquid mist and the deionized water mist are allowed toreach the substrate W with their velocity less attenuated.

[0200] In the present substrate processing apparatus 1001, the removerliquid mist and the deionized water mist from the remover liquid spraynozzle 1012 and the deionized water spray nozzle 1025 are sprayed withan angle of 45 degrees with respect to the surface of the substrate W.In general, each of them can be discharged in a direction tilted fromthe normal direction to the substrate W. In order to properly remove thereaction products of the side walls, the angle between the dischargingdirection of the remover liquid mist and the deionized water mist andthe surface of the substrate W is preferably set in the range of notless than 30 degrees to not more than 60 degrees, in particular, at 45degrees.

[0201] <5. Substrate Processing Method Using the Substrate ProcessingApparatus 1001>

[0202] As illustrated in FIG. 4, the present substrate processing methodusing the substrate processing apparatus 1001 includes a remover liquidsupplying step s1001, a remover liquid spinning-off step s1002, adeionized water supplying step s1003, and a deionized water spinning-offstep s1004. Referring to FIG. 4, the following description will discussthe respective steps.

[0203] In FIG. 4, the described respective elements are plotted on theaxis of ordinates and the described times are plotted on the axis ofabscissas. With respect to the valves, the opened state is indicatedwith hatching and with respect to the other factors, the operative stateis indicated with hatching.

[0204] (1. Remover Liquid Supplying Step s1001)

[0205] First, the control means 1069 has controlled thetemperature-adjusting devices 1051 and 1061 so that the temperatures ofthe remover liquid and deionized water are set to predeterminedtemperatures before the sequence has reached the time t1000.

[0206] Moreover, before the sequence has reached the time t1000, thecontrol means 1069 drives the spin motor 1013 to rotate the substrate Wso that at the time t1000, the substrate W is being rotated at apredetermined number of revolutions.

[0207] Then at the time t1000, the control means 1069 rotates the firstrotary motor 1017.

[0208] Furthermore, at the time t1000, the control means 1069 drives theremover liquid pump 1047 with the remover liquid discharging valve 1058being opened so that the remover liquid is supplied to the substrate Wfrom the remover liquid discharging nozzle 1011. Thus, the substrate Wis supplied with a comparatively large amount of the remover liquid,with the result that the reaction products on the substrate W start toswell.

[0209] Next, after a lapse of a first predetermined time period fromtime t1000, the remover liquid discharging valve 1058 is closed to stopthe supply of the remover liquid from the remover liquid dischargingnozzle 1011, while the remover liquid spray valve 1053 and the removerliquid side nitrogen valve 1066 are opened so that the remover liquidmist is sprayed from the remover liquid spray nozzle 1012 onto thesubstrate W. Thus, the remover liquid mist, which has been acceleratedto approximately sound velocity, is sprayed onto the reaction productsthat are swelling and softening. Thus, the remover liquid is firmlydriven into the reaction products, thereby allowing the reactionproducts to further swell, and the swelled reaction products come offthe substrate W.

[0210] Moreover, since the remover liquid spray nozzle 1012 sprays theremover liquid mist with an angle of 45 degrees with respect to thesubstrate W, the remover liquid mist is allowed to reach the reactionproducts adhering to the irregular side walls of the substrate W withoutbeing weakened in its force against the reaction products. Consequently,it is possible to further accelerate the swelling and coming off of thereaction products from the substrate W.

[0211] The first predetermined time period is a period of time from thetime t1000 to the time at which the reaction products on the substrate Wstart to swell by the remover liquid supplied from the remover liquiddischarging nozzle 1011, and this has been preliminarily found throughexperiments.

[0212] Then, at the time t1001, the control means 1069 stops the drivingoperation of the first rotary motor 1017 with the remover liquid spraynozzle 1012 having retreated from a position above the cup 1003.Moreover, the control means 1069 closes the remover liquid spray valve1053 and the remover liquid side nitrogen valve 1086, and also stops thedriving operation of the remover liquid pump 1047 so as to stop thesupply of the remover liquid from the remover liquid supplying section1007.

[0213] (2. Remover Liquid Spinning-Off Step s1002)

[0214] Next, at the time t1001, the control means 1069 stops the supplyof the remover liquid to the substrate W, while it successively rotatesthe spin motor 1013 so as to maintain the rotating state of thesubstrate W. Thus, a remover liquid spinning-off step s1002 is executed.

[0215] In this remover liquid spinning-off step s1002, the substrate Wis rotated at not less than 500 rpm, more preferably, in the range from1000 rpm to 4000 rpm.

[0216] Moreover, the time during which the rotation is maintained is setto not less than 1 second, preferably, in the range of 2 to 5 seconds.

[0217] In this manner, the rotating state of the substrate is maintainedwith the supply of the remover liquid being stopped with respect to thesubstrate W, the remover liquid on the substrate W is spun off from thesubstrate W by a centrifugal force.

[0218] (3; Deionized Water Supplying Step s1003)

[0219] At the time t1002, the control means 1069 rotates the secondrotary motor 1031.

[0220] At the time t1002 also, the control means 1069 drives thedeionized water pump 1057 so as to supply deionized water from thedeionized water discharging nozzle 1024 with the deionized waterdischarging valve 1058 being open. Thus, the substrate W is suppliedwith a comparatively large amount of deionized water so that thereaction products that have swelled on the substrate W start to bewashed away.

[0221] Next, after a lapse of a second predetermined time period fromthe time t1002, the deionized water discharging valve 1058 is closed tostop the supply of the deionized water from the deionized waterdischarging nozzle 1024, while the deionized water spray valve 1053 andthe deionized water side nitrogen valve 1065 are opened so that thedeionized water mist is sprayed from the deionized water spray nozzle1025 onto the substrate W. Thus, the deionized water mist, which hasbeen accelerated to approximately sound velocity, is sprayed onto thereaction products that are swelling and softening, with the result thatthe reaction products come off the substrate W.

[0222] Moreover, since the deionized water spray nozzle 1025 sprays thedeionized water mist with an angle of 45 degrees with respect to thesubstrate W, the deionized water mist is allowed to reach the reactionproducts adhering to the irregular side walls of the substrate W withoutbeing weakened in its force against the reaction products. Consequently,it is possible to further accelerate the coming off of the reactionproducts from the substrate W. In general, the mist can be discharged ina direction tilted from the normal to the substrate W.

[0223] The second predetermined time period is a period of time from thetime t1002 to the time at which the reaction products on the substrate Whave come off to a certain degree by the deionized water supplied fromthe deionized water discharging nozzle 1024, and this has beenpreliminarily found through experiments.

[0224] Then, at the time t1003, the control means 1069 stops the drivingoperation of the second rotary motor 1031 with the deionized water spraynozzle 1025 having retreated from a position above the cup 1003.Moreover, the control means 1069 closes the deionized water spray valve1053 and the deionized water side nitrogen valve 1065, and also stopsthe driving operation of the deionized water pump 1057 so as to stop thesupply of the deionized water from the deionized water supplying section1009.

[0225] (4. Deionized Water Spinning-Off Step s1004)

[0226] At the time t1003, the control means 1069 stops the supply of thedeionized water to the substrate W, while it successively rotates thespin motor 1013 so as to maintain the rotating state of the substrate W.Thus, a deionized water spinning-off step s1004 is executed.

[0227] In this manner, by supplying the remover liquid and deionizedwater to the substrate W, the reaction products are removed therefrom.

[0228] In accordance with the present substrate processing method, untilthe first predetermined time period has elapsed since the start of theremover liquid supplying step s1001, dense current of the liquid-stateremover liquid is continuously supplied from the remover liquiddischarging nozzle 1011, however, after the lapse of the firstpredetermined time, the remover liquid mist is supplied from the removerliquid spray nozzle 1012. Thus, in comparison with a case in which densecurrent (non-mist current) of the remover liquid is continuouslysupplied from the remover liquid discharging nozzle 1011 for the entireremover liquid supplying process s1001, it is possible to reduce theamount of consumption of the remover liquid. Moreover, since thehigh-speed remover liquid mist is discharged from the remover liquidspray nozzle 1012, the time required for the swelling of the reactionproducts on the substrate W and coming-off thereof from the substrate Wis shortened, thereby making it possible to improve the throughput.

[0229] Furthermore, until the second predetermined time period haselapsed since the start of the deionized water supplying step s1003,dense current of the deionized water is continuously supplied from thedeionized water discharging nozzle 1024, however, after the lapse of thesecond predetermined time period, the deionized water mist is suppliedfrom the deionized water spray nozzle 1025. Thus, in comparison with acase in which dense current of the deionized water is continuouslysupplied from the deionized water discharging nozzle 1024 for the entiredeionized water supplying process s1003, it is possible to reduce theamount of consumption of the deionized water. Moreover, since thehigh-speed deionized water mist is discharged from the deionized waterspray nozzle 1025, the time period required for the coming-off of thereaction products from the substrate W is shortened, thereby making itpossible to improve the throughput.

[0230] In accordance with the present substrate processing method, atthe remover liquid spinning-off step s1002, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W becomes very little, or no longer exists. Therefore, in thecase when, in this state, the deionized water is supplied to thesubstrate W at the deionized water supplying step s1003, the amount ofthe remover liquid that comes to contact the deionized water becomesvery little or none. Therefore, even in the event of a pH shock, hardlyany adverse effect is given to the substrate W, or no pH shock occurs.

[0231] Moreover, in the present substrate processing method, until thefirst predetermined time period has elapsed since the time t1000, densecurrent of the remover liquid is supplied from the remover liquiddischarging nozzle 1011, and up to the time t1001 after the lapse of thefirst predetermined time, the remover liquid mist is sprayed onto thesubstrate W from the remover liquid spray nozzle 1012. Instead of thisarrangement, the following method may be adopted.

[0232] That is, the remover liquid mist may be supplied from the removerliquid spray nozzle 1012 from the time t1000 to the time t1001. In thiscase, it is not necessary to install the remover liquid dischargingnozzle 1011 in the substrate processing apparatus 1001.

[0233] Moreover, until a predetermined time period has elapsed from thetime t1000, the remover liquid mist may be supplied from the removerliquid spray nozzle 1012, and after the lapse of the predetermined timeperiod, dense current of the remover liquid may be supplied from theremover liquid discharging nozzle 1011.

[0234] In the present substrate processing method, until the secondpredetermined time period has elapsed since the time t1002, densecurrent of the deionized water is supplied from the deionized waterdischarging nozzle 1024, and up to the time t1003 after the lapse of thesecond predetermined time period, the deionized water mist is sprayedonto the substrate W from the deionized water spray nozzle 1025,however, instead of this arrangement, the following method may beadopted.

[0235] That is, the deionized water mist may be supplied from thedeionized water spray nozzle 1025 from time t1002 to time t1003. In thiscase, it is not necessary to install the deionized water dischargingnozzle 1024 in the substrate processing apparatus 1001.

[0236] Moreover, until a predetermined time period has elapsed from thetime t1002, the deionized water mist may be supplied from the deionizedwater spray nozzle 1025, and after the lapse of the predetermined timeperiod, the liquid-state deionized water may be supplied from thedeionized water discharging nozzle 1024.

[0237] <6. Substrate Processing Apparatus 1100>

[0238] Referring to FIGS. 8 and 9, an explanation will be given of asubstrate processing apparatus 1100. FIG. 9 is a cross-sectional viewtaken along line F9-F9 of FIG. 8; and, for convenience of explanation,hatching is omitted from some portions.

[0239] The substrate processing apparatus 1100 is provided with asolvent supplying section 1002 serving as an intermediate rinsesupplying section, in addition to the aforementioned substrateprocessing apparatus 1001. The substrate processing apparatus 1100 hasmany parts that are in common with the substrate processing section1001. Therefore, the same parts as the substrate processing apparatus1001 are indicated by the same reference numerals, and the descriptionthereof is omitted.

[0240] The substrate processing apparatus 1100 has the solvent supplyingsection 1002, and the solvent supplying section 1002, which is securedto the apparatus frame is provided with a third rotary motor 1018 havinga driving shaft placed in the vertical direction, a third rotary shaft1020 secured to the rotary shaft of the third rotary motor 1018 and athird arm 1022 connected to the top of the third rotary shaft 1020.

[0241] A solvent discharging nozzle 1040 is installed on the tip of thethird arm 1022. The solvent discharging nozzle 1040 is a tube-shapedmember with its length direction set virtually in the verticaldirection, and an organic solvent is supplied to one end thereof withthe other end supplying the organic solvent to the substrate W.

[0242] Moreover, a solvent spray nozzle 1039 is attached to the same tipof the third arm 1022 through a bracket 1041 (indicated by an alternatelong and two short dashes line in FIG. 9). The solvent spray nozzle1039, which sprays a solvent mist as will be described later, isarranged so as to spray the solvent mist with an inclination of 45degrees with respect to the surface of the substrate W.

[0243] The solvent discharging nozzle 1040 and solvent spray nozzle 1039are arranged so that the organic solvent discharged from the organicsolvent discharging nozzle 1040 and the solvent mist sprayed from thesolvent spray nozzle 1039 are allowed to intersect each other on thesurface of the substrate W, and so that, when the solvent dischargingnozzle 1040 and the solvent spray nozzle 1039 are allowed to pivot bythe third rotary motor 1018, the organic solvent discharged from thesolvent discharging nozzle 1040 and the solvent mist sprayed from thesolvent spray nozzle 1039 are reciprocally shifted, as illustrated inFIG. 9, on a circular arc 1086 that passes through the rotation center Cof the substrate W and also intersects a rotation circle 1095 that theend edge of the rotating substrate W forms at two points on thecircumference thereof.

[0244] The gas-liquid mixing nozzle 1027 shown in FIG. 3 is used as thesolvent spray nozzle 1039, and pressurized nitrogen gas is supplied tothe gas introducing tube 1038 from a nitrogen supplying system 1094,which will be described later, and an organic solvent is supplied from asolvent supplying system 1090 to the process liquid introducing tube1029. Thus, the solvent mist is sprayed from the solvent spray nozzle1039.

[0245] <7. Solvent Supplying System>

[0246]FIG. 11 shows the solvent supplying system 1090 and the nitrogensupplying system 1094.

[0247] The solvent supplying system 1090 is provided with a solvent pump1048 for pumping the organic solvent from an organic solvent source 1046outside the apparatus, a temperature-adjusting device 1050 for adjustingthe temperature of the organic solvent by heating or cooling the organicsolvent pumped out by the solvent pump 1048 to a predeterminedtemperature, a filter 1052 for filtering contaminants from the organicsolvent that has been temperature-adjusted by the temperature-adjustingdevice 1050, and a solvent spray valve 1054 for opening and closing theflowing path of the filtered organic solvent to the organic solventspray nozzle 1039.

[0248] This arrangement allows the solvent supplying system 1090 tosupply the organic solvent that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 1050 andpurified by the filter 1052 to the organic solvent spray nozzle 1012.

[0249] Moreover, the solvent supplying system 1090 also has a solventdischarging valve 1062 for opening and closing the flowing path of theorganic solvent having been filtered to a solvent discharging nozzle1040, and the discharging and discharge-stopping operations of theorganic solvent from the solvent discharging nozzle 1040 are controlledby opening and closing the solvent discharging valve 1062.

[0250] The nitrogen supplying system 1094 is provided with a nitrogensource 1068 for supplying pressurized nitrogen gas, a remover liquidside nitrogen valve 1066 for opening and closing the tube path from thenitrogen source 1068 to the remover liquid spray nozzle 1012, adeionized water side nitrogen valve 1065 for opening and closing thetube path from the nitrogen source 1068 to the deionized water spraynozzle 1025, and a solvent side nitrogen valve 1071 for opening andclosing the tube path toward the solvent spray nozzle 1039. Thus, thesupplying and supply-stopping operations of nitrogen gas to the removerliquid spray nozzle 1012 are controlled by opening and closing theremover liquid side nitrogen valve 1066, the supplying andsupply-stopping operations of nitrogen gas to the deionized water spraynozzle 1025 are controlled by opening and closing the deionized waterside nitrogen valve 1065, and the supplying and supply-stoppingoperations of nitrogen gas to the solvent spray nozzle 1039 arecontrolled by opening and closing the solvent side nitrogen valve 1071.

[0251] Moreover, the substrate processing apparatus 1100 has a controlmeans and in the same manner as the control means 1069 of the substrateprocessing apparatus 1001, to the control means are connected the spinmotor 1013, the first rotary motor 1017, the second rotary motor 1031,the remover liquid pump 1047, the deionized water pump 1057, the removerliquid spray valve 1053, the deionized water spray valve 1083, theremover liquid discharging valve 1056, the deionized water dischargingvalve 1058, the remover liquid side nitrogen valve 1066, the deionizedwater side nitrogen valve 1065, the temperature-adjusting device 1051and the temperature-adjusting device 1061, and to the control means arefurther connected the third rotary motor 1018, the solvent pump 1048,the solvent spray valve 1054, the solvent discharging valve 1062, thesolvent side nitrogen valve 1071 and the temperature-adjusting device1050.

[0252] In the present substrate processing apparatus 1100, thegas-liquid mixing nozzle 1027 is used as the solvent spray nozzle 1039.Since the gas-liquid mixing nozzle 1027 has the straight flow section1037, the dispersion of the solvent mist is regulated. For this reason,the solvent mist is accelerated to a predetermined velocity, and thesolvent mist is allowed to reach the substrate W with its velocity beingless attenuated.

[0253] In the present substrate processing apparatus 1100, the solventspray nozzle 1039 discharges the solvent mist with an angle of 45degrees with respect to the surface of the substrate W. In general, itcan be discharged in a direction tilted from the normal direction to thesubstrate W, in order to properly remove the reaction products on sidewalls, the angle between the discharging direction of the solvent mistand the top major surface of the substrate W is preferably set in therange of 30 degrees to 60 degrees, more preferably, at 45 degrees.

[0254] <8. Substrate Processing Method Using the Substrate ProcessingApparatus 1100>

[0255] Referring to FIG. 10, an explanation will be given of a substrateprocessing method in which the above-mentioned substrate processingapparatus 1100 is used.

[0256] The present substrate processing method using the substrateprocessing apparatus 1100 includes a remover liquid supplying steps1031, a remover liquid spinning-off step s1032, a solvent supplyingstep s1033 serving as an intermediate rinse-process, a deionized watersupplying step s1034, and a deionized water spinning-off step s1035.

[0257] The present substrate processing method is virtually the same asthe substrate processing method using the substrate processing apparatus1001 having the remover liquid supplying step s1001, the remover liquidspinning-off step s1002, the deionized water supplying step s1003 andthe deionized water spinning-off step s1004, except that the solventsupplying step is interpolated between the remover liquid spinning-offstep s1002 and the deionized water supplying step s1003.

[0258] Therefore, the above-mentioned remover liquid supplying steps1031, the remover liquid spinning-off step s1032, the deionized watersupplying step s1034 and the deionized water spinning-off step s1035 arerespectively the same as the remover liquid supplying step s1001, theremover liquid spinning-off step s1002, the deionized water supplyingstep s1003 and the deionized water spinning-off step s1004 in thesubstrate processing method using the substrate processing apparatus1001. Therefore, the description thereof is omitted.

[0259] Next, referring to FIG. 12, the following description willdiscuss the solvent supplying process s1033. In FIG. 12, the describedrespective elements are plotted on the axis of ordinates and thedescribed times are plotted on the axis of abscissas. With respect tothe valves, the opened state is indicated with hatching, and withrespect to the other factors, the operative state is indicated withhatching.

[0260] The solvent supplying step s1033 is carried out after the removerliquid supplying step s1031 and the remover liquid spinning-off steps1032 have been finished. In the remover liquid spinning-off step s1032,the substrate is kept rotating with the supply of the remover liquid tothe substrate W being stopped so that the remover liquid on thesubstrate W is spun off from the substrate W by a centrifugal force.Thus, the remover liquid remaining on the substrate W is reduced to aminimum.

[0261] At the time t1002, the control mean rotates the third rotarymotor 1018.

[0262] At the time t1002 also, the control means drives the solvent pump1048 so as to supply the organic solvent from the solvent dischargingnozzle 1040, with the solvent discharging valve 1062 being opened. Thus,the substrate W is supplied with a comparatively large amount of theorganic solvent so that the remover liquid on the substrate W starts tobe washed away.

[0263] Next, after a lapse of a third predetermined time period sincethe time t1002, the solvent discharging valve 1062 is closed so that thesupply of the organic solvent from the solvent discharging nozzle 1040is stopped, and the solvent spray valve 1054 and the solvent sidenitrogen valve 1071 are opened so that the solvent mist is sprayed fromthe solvent spray nozzle 1039 toward the substrate W. Thus, the solventmist, which has been accelerated to approximately sound velocity, issprayed onto the reaction products that have swelled and softened, withthe result that the reaction products come off from the substrate W.

[0264] Moreover, since the solvent spray nozzle 1039 sprays the solventmist with an angle of 45 degrees with respect to the major surface ofthe substrate W, the solvent mist is allowed to reach the reactionproducts adhering to the irregular side walls of the substrate W withoutbeing weakened in its force against the reaction products. Consequently,it is possible to further accelerate the swelling and coming-off of thereaction products from the substrate W. Thus, it becomes possible toshorten the time required for the process. In general, the mist can bedischarged in a direction tilted from the normal to the substrate W.

[0265] The third predetermined time period is a period of time from thetime t1002 to the time at which the remover liquid on the substrate Whas been washed away to a certain degree by the organic solvent suppliedfrom the solvent discharging nozzle 1040, and this has beenpreliminarily found through experiments.

[0266] Then, at the time t1003, the control means stops the drivingoperation of the third rotary motor 1018 with the solvent spray nozzle1039 having retreated from a position above the cup 1003. Moreover, thecontrol means closes the solvent spray valve 1054 and the solvent sidenitrogen valve 1071, and also stops the driving operation of the solventpump 1048 so as to stop the supply of the organic solvent from thesolvent spray nozzle 1039.

[0267] In this manner, in the solvent supplying step s1033, the organicsolvent is supplied to the substrate W so that the remover liquid iswashed away from the substrate W. For this reason, even when deionizedwater is supplied to the substrate W in the succeeding deionized watersupplying step s1034, no remover liquid contacting the deionized waterexists, thereby making it possible to prevent the occurrence of a pHshock. Consequently, it is possible to prevent the resulting damages tothe thin films on the substrate W.

[0268] In accordance with the present substrate processing method, atthe remover liquid spinning-off step s1032, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W at this point of time is very little. For this reason, it ispossible to shorten the time required for the organic solvent to removethe remover liquid at the solvent supplying step s1033. Thus, it ispossible to improve the throughput. In the same manner, since theremover liquid remaining on the substrate W is very little, it ispossible to reduce the amount of the organic solvent required for thesolvent supplying process s1033, and consequently to reduce the costs.

[0269] In the present substrate processing method, immediately after thesolvent supplying step s1033, the deionized water supplying processs1034 is executed. However, a solvent spinning-off step for spinning thesolvent off from the substrate W may be interpolated between the solventsupplying step s1033 and the deionized water supplying step s1034.

[0270] Moreover, in the present substrate processing method, therotation of the substrate W has not been stopped from the start of theremover liquid supplying step s1031 to the completion of the deionizedwater spinning-off step s1035. However, the rotation of the substrate Wmay be stopped in any one of the intervals between the remover liquidsupplying step s1031 and the remover liquid spinning-off step s1032,between the remover liquid spinning-off step s1032 and the solventsupplying step s1033, between the solvent supplying step s1033 and thedeionized water supplying step s1034, and between the deionized watersupplying step s1034 and the deionized water spinning-off process s1035.

[0271] Moreover, in the present substrate processing method, until thefirst predetermined time has elapsed since time t1000, the liquid-stateremover liquid is supplied from the remover liquid discharging nozzle1011, and up to time t1001 after the lapse of the first predeterminedtime, the remover liquid mist is sprayed onto the substrate W from theremover liquid spray nozzle 1012. However, instead of this arrangement,the following method may be adopted.

[0272] That is the remover liquid mist may be supplied from the removerliquid spray nozzle 1012 from the time t1000 to the time t1001. In thiscase, it is not necessary to install the remover liquid dischargingnozzle 1011 in the substrate processing apparatus 1100.

[0273] Moreover, until a predetermined time has elapsed from the timet1000, the remover liquid mist may be supplied from the remover liquidspray nozzle 1012, and up to the time t1001 after the lapse of thepredetermined time, the liquid-state remover liquid may be supplied fromthe remover liquid discharging nozzle 1011.

[0274] Moreover, in the present substrate processing method, until thethird predetermined time period has elapsed since the time t1002, theliquid-state organic solvent is supplied from the solvent dischargingnozzle 1040, and up to the time t1003 after the lapse of the thirdpredetermined time, the solvent mist is sprayed onto the substrate Wfrom the solvent spray nozzle 1039. However, instead of thisarrangement, the following method may be adopted.

[0275] That is, the solvent mist may be supplied from the solvent spraynozzle 1039 from the time t1002 to the time t1003. In this case, it isnot necessary to install the solvent discharging nozzle 1040 in thesubstrate processing apparatus 1100. Moreover, until a predeterminedtime has elapsed from the time t1002, the solvent mist may be suppliedfrom the solvent spray nozzle 1039, and up to the time t1003 after thelapse of the predetermined time period, organic solvent in the form ofdense-liquid current may be supplied from the solvent discharging nozzle1040.

[0276] Moreover, in the present substrate processing method, until thesecond predetermined time period has elapsed since time t1002, theliquid-state deionized water is supplied from the deionized waterdischarging nozzle 1024, and up to the time t1004 after the lapse of thesecond predetermined time period, the deionized water mist is sprayedonto the substrate W from the deionized water spray nozzle 1025.However, instead of this arrangement, the following method may beadopted.

[0277] That is, the deionized water mist may be supplied from thedeionized water spray nozzle 1025 from the time t1003 to the time t1004.In this case, it is not necessary to install the deionized waterdischarging nozzle 1024 in the substrate processing apparatus 1100.

[0278] Moreover, until a predetermined time period has elapsed from thetime t1003, the deionized water mist may be supplied from the deionizedwater spray nozzle 1025, and up to the time t1 004 after the lapse ofthe predetermined time period, dense-current of the deionized water maybe supplied from the deionized water discharging nozzle 1024.

[0279] Furthermore, in the present preferred embodiment, a sequence ofprocesses including the remover liquid supplying step s1031, the removerliquid spinning-off step s1032, the solvent supplying step s1033, thedeionized water supplying step s1034 and the deionized waterspinning-off step s1035 is carried out only once. However, this sequenceof processes may be repeated several times.

[0280] <9. Supplement>

[0281] In the above-mentioned substrate processing apparatuses 1001,1100, the holding rotary section rotates the substrate while maintainingit horizontally. However, the holding rotary section may rotate thesubstrate with its major surface being tilted with respect thehorizontal plane, or may rotate the substrate with its major surfacebeing maintained in the vertical direction.

[0282] Moreover, in the above-mentioned substrate processing apparatuses1001, 1100, the holding rotary section holds only one substrate.However, the holding rotary section may be designed to hold a pluralityof substrates.

[0283] In the above-mentioned substrate processing apparatuses 1001,1100, nitrogen gas supplying systems 1093, 1094 for supplying nitrogengas to the remover liquid spray nozzle 1012, the deionized water spraynozzle 1025 and the solvent spray nozzle 1039 are installed. Instead ofthe nitrogen sources 1067, 1068 of the nitrogen supplying systems 1093,1094, pressurized air sources for supplying pressurized air may beinstalled, and instead of the nitrogen supplying systems 1093, 1094,pressurized air supplying systems may be installed. In this case, theprocess liquid mists are formed by pressurized air.

[0284] Moreover, in the above-mentioned substrate processing apparatuses1001, 1100, nitrogen gas is supplied to the remover liquid spray nozzle1012, the deionized water spray nozzle 1025 and the solvent spray nozzle1039 so that when the process liquid mists are supplied to the substratehaving metal films, it is possible to prevent oxidation of the metalfilms, and consequently to reduce degradation in the quality of theprocessed substrate. Example of the metal films include aluminum films.In particular, in the case of copper (Cu) that is easily oxidized, thepresent invention is effectively applied to a substrate having copperfilms. In this case, an inert gas such as argon may be used in place ofnitrogen gas with the same effects.

[0285] In the substrate processing apparatus 1001, the gas-liquid mixingnozzle 1027 is applied to both of the remover liquid supplying section1007 and the deionized water supplying section 1009. This may be appliedto either of them.

[0286] Moreover, in the substrate processing apparatus 1100, thegas-liquid mixing nozzle 1027 is applied to all the three parts, thatis, the remover liquid supplying section 1007, the deionized watersupplying section 1009 and the solvent supplying section 1002. This maybe applied to any one or any two of them.

[0287] Furthermore, in the above-mentioned substrate processingapparatuses 1001, 1100, the substrate treatment deals with a substratehaving a surface on which polymers are formed through dry-etching. Thepresent substrate treatment is more effectively applied to a substratethat has been further subjected to ashing after the dry-etching.

[0288] The ashing is carried out with a substrate having a resist filmbeing placed in an oxygen plasma, and after the ashing, more polymersare generated. For this reason, in the case when a process for removingpolymers from the substrate that has been subjected to the dry-etchingand ashing, the present invention makes it possible to further improvethe throughput, and to reduce the costs more effectively.

[0289] In the above-mentioned substrate processing apparatuses 1001,1100, even in the case when the reaction products are accumulated on thesubstrate W in a protruding form, the process liquid mist is dischargedonto the substrate W in a direction tilted with respect to the substrateW so that the reaction products, accumulated in the protruding form, isbroken by the process liquid mist that is discharged thereto with highspeeds. For this reason, it is possible to finish the removing processof the reaction products more quickly.

[0290] (B. Preferred Embodiments According to Second Aspect of thePresent Invention)

[0291] <1. First Preferred Embodiment>

[0292]FIG. 13 is a block diagram that shows a schematic construction ofa substrate cleaning device in accordance with the present preferredembodiment, and FIG. 14 is a plan view thereof.

[0293] In the Figures, reference numeral 2001 is a disc-shaped spinchuck, and six support pins 2001 a are attached to the spin chuck 2001in a protruding manner. As illustrated in FIG. 13, the spin chuck 2001is allowed to rotate by an electric motor 2005 through a rotary shaft2003 connected to the bottom surface thereof. A substrate W, which issupported by the support pins 2001 a contacting the circumferential edgethereof, is rotated within a horizontal plane around the rotation centerPa by this rotative driving operation. A scattering preventive cup 2009for preventing the scattering of a cleaning liquid M discharged from adouble fluids cleaning nozzle 2007 is placed on the periphery of thespin chuck 2001. The cleaning liquid may be remover liquid for removingresidual pollution from the surface of the substrate. This scatteringpreventive cup 2009 is designed to be raised and lowered with respect tothe spin chuck 2001 as indicated by arrow shown in the Figure at thetime when an uncleaned substrate W is placed on the spin chuck 2001 orwhen a transport means, not shown, receives a cleaned substrate W fromthe spin chuck 2001.

[0294] As illustrated in FIG. 13, the cleaning nozzle 2007 is supportedwith its trunk portion 2007 b connected to the tip of a support arm 2008so that its discharging surface 2007 a is directed to the surface of thesubstrate W. The base portion of the support arm 2008 is, on the otherhand, connected to a raising and shifting mechanism 11. As illustratedin FIG. 14, the cleaning nozzle 2007 is directed to a supply finishposition F through the rotation center Pa from the supply start positionK of the cleaning liquid within the in-plane of the substrate W.Moreover, a rotary shaft 2011 b of a rotary motor 2011 a is connected tothe support arm 2008. This is used for rocking the cleaning nozzle 2007around the rotation center Pb of the rotary motor 2011 a on thesubstrate W.

[0295] Moreover, the cleaning nozzle 2007 constitutes two fluids nozzlein which a pipe 20015 a for introducing compressed air into its trunkportion 2007 b as gas and a pipe 2015 d for introducing deionized wateras liquid are connected and allowed to communicate with each other. Thepipe 2015 a is connected to a compressed air supplying section 2021corresponding to a gas supplying means of the present invention on theupstream side thereof. The pipe 2015 a is provided with anelectropneumatic regulator 2017 a for adjusting the pressure oftransmitted air to a pressure corresponding to a control signal inputtedfrom a controller 2020, a pressure sensor 2018 a for detecting thepressure of air and a flow-rate sensor 2019 a for detecting the flowrate.

[0296] Moreover, the pipe 2015 b is provided with an electropneumaticregulator 2017 b for adjusting the pressure of transmitted deionizedwater to a pressure corresponding to a control signal inputted from thecontroller 2020, a pressure sensor 2018 b for detecting the pressure ofair and a flow-rate sensor 2019 b for detecting the flow rate. Theliquid to be used is not limited to deionized water, and, for example,extra-pure water (extra-deionized water) may be used. Moreover, any oneof chemical liquids (for example, hydrofluoric acid, sulfuric acid,hydrochloric acid, nitric acid, phosphoric acid, acetic acid, ammonia ora hydrogen peroxide water liquid of these) may be used.

[0297] Control signals from the controller 2020 are respectivelyinputted to the electropneumatic regulators 2017 a, 2017 b, and inaccordance with these control signals, the pressures of the gas anddeionized water transmitted through the pipes 2015 a, 2015 b areadjusted. The results of detection, successively detected by thepressure sensors 2018 a, 2018 b and the flow-rate sensors 2019 a, 2019b, are fed back to the controller 2020.

[0298] To the controller 2020 are respectively connected the electricmotor 2005, the raising and shifting mechanism 2011, theelectropneumatic regulators 2017 a, 2017 b, the pressure sensors 2018 a,2018 b and the flow-rate sensors 2019 a, 2019 b. Cleaning conditions foreach substrate W are preliminarily stored in the controller 2020 as acleaning program (also referred to as “recipe”), and the above-mentionedrespective sections are controlled in accordance with the cleaningprogram for each substrate W.

[0299] Moreover, an instructing section 2030, which is used for formingand altering the cleaning programs and for selecting a desired one of aplurality of cleaning programs, is connected to the controller 2020.

[0300] Next, referring to Figures, a detailed explanation will be givenof the inner structure of the cleaning nozzle 2007 that is the featuredconstruction of the present preferred embodiment. FIG. 15 is across-sectional side view taken from the apparatus side, whichschematically shows the structure of the cleaning nozzle 2007.

[0301] In this structure, the trunk portion 2007 b is secured to one endof the support arm 2008 with bolts, etc., and placed with a gasdischarging nozzle 2100 having a gas discharging outlet 2101 and aliquid discharging nozzle 2200 having a liquid discharging outlet 2201being inserted through the inside of the trunk portion 2007 b. The gasdischarging nozzle 2100 and the liquid discharging nozzle 2200 areconnected to the compressed air supplying section 2021 and the deionizedwater supplying section 2025 through the pipes 2015 a, 2015 b that passthrough the inside of the support arm 2008.

[0302] The gas discharging nozzle 2100, which is placed in a manner soas to allow its gas discharging outlet 2101 to face the surface of thesubstrate W, is arranged so that its center axis line P1 passing throughthe gas discharging outlet 2101 is allowed to vertically cross thesurface of the substrate W. The liquid discharging nozzle 2200 is, onthe other hand, placed in a manner so as to diagonally tilt in thevicinity of the gas discharging nozzle 2100, and arranged so that itscenter axis line P2 passing through the liquid discharging outlet 2201is allowed to diagonally cross the surface of the substrate W. Thecrossing point at which the center axis lines P1, P2 intersect eachother is a collision portion G that is a mixing area between the liquidand gas. This mixing area between the liquid and the gas is within theopen space.

[0303] The trunk portion 2007 b of the cleaning nozzle 2007 has a columnshape with its outer circumferential edge of the discharging surface2007 a forming a beveled portion 2007 c sticking downward. The gasdischarging nozzle 2100 is arranged so that the gas discharging outlet2101 is placed on the upper surface portion 2007 d of the beveledportion 2007 c, and the liquid discharging nozzle 2200 is arranged sothat the liquid discharging outlet 2201 is placed in the mid point ofthe beveled portion 2007 c. Additionally, the trunk portion 2007 b isintegrally formed by a fluoro-resin such as Teflon.

[0304] Next, in an attempt to form atomized cleaning liquid by using thecleaning nozzle 2007, the incident angle α of each of the center axislines P1, P2 in the collision portion G is preferably set in the rangeof not less than 0 degree to not more than 110 degrees, although itslightly changes depending on the flow rate and flow velocity of eachfluid. In this case, when the respective incident angles α are set to 0degree, the discharging directions of air and deionized water are inparallel with each other, however, by discharging one of the dischargedflows into the jet flow of the other, it is possible to form droplets ormist. With respect to its aspect, a detailed explanation will be givenlater in a second preferred embodiment. However, in the case when theincident angle α is greater than 110 degrees, the collision betweendeionized water and air virtually becomes a frontal collision, andconsequently, it is confirmed that the droplets are scattered not in onedirection, but in all the directions. In other words, the droplets thatare directed to the surface of the substrate so as to clean the surfaceof the substrate W come to decrease in number, failing to carry out agood cleaning operation. Therefore, the incident angle α is preferablyset in the range of not less than 0 degree to not more than 110 degreesso that it becomes possible to direct the atomized cleaning liquid inone direction.

[0305] Moreover, with respect to the distance β from the liquiddischarging outlet 2201 to the collision portion G is preferably set inthe range from greater than 0 mm to not more than 20 mm as a distancethat does not allow the pressure of the liquid discharged flow toattenuate to cause the flow to collapse.

[0306] Moreover, the collision portion G is set at the same position asthe discharging surface 2007 a of the cleaning nozzle 2007 or at aposition slightly closer to the surface side of the substrate W. Withthis arrangement, the beveled portion 2007 c is allowed to preventexternal influences at the collision portion G, thereby making itpossible to properly mix deionized water and air. Since the collisionportion G is not close to the upper surface portion 2007 d, it ispossible to prevent the atomized droplets from adhering to the innersurface of the beveled portion 2007 c and dropping therefrom. Thedistance between the collision portion G and the surface of thesubstrate W is preferably set in accordance with a desired cleaningcapability, and it is set to not more than 100 mm, preferably,approximately in the range of 3 to 30 mm.

[0307] In the above-mentioned arrangement, when the electropneumaticregulators 2017 a, 2017 b are released by signals from the controller2020 so that air and deionized water are supplied from the gasdischarging outlet 2101 and the liquid discharging outlet 2201, thedeionized water is mixed into the discharged flow or jet of air thusinjected into the open space around the portion G so as to allow thedischarged flow structure to collapse, thereby accelerating theformation of the droplets. This atomized cleaning liquid makes itpossible to clean the surface of the substrate W.

[0308] Next, an explanation will be given of the cleaning operationcarried out by the substrate cleaning device having the above-mentionedstructure.

[0309] First, a predetermined cleaning program corresponding to thesubstrate W is selected by the instructing section 2030, and executed.Then, the scattering preventive cup 2009 is lowered with respect to thespin chuck 2001, and a substrate W is carried into the substratecleaning device by a hand of a substrate transporting robot with thecleaning nozzle 2007 being located at a stand-by position. Thus, it isplaced on the upper surface of the spin chuck 2001, and held thereon.Further, the scattering preventive cup 2009 is raised, while thecleaning nozzle 2007 is shifted to a cleaning start position. Next, thespin chuck 2001 holding the substrate W is rotated, thereby allowing thesubstrate W to rotate in the rotation direction, centered on therotation center Pa (substrate rotating step).

[0310] Next, as illustrated in FIG. 14, with the substrate W beingrotated at a fixed low speed, the cleaning nozzle 2007 is allowed toshift from the supply start position K of the cleaning liquid to thesupply end position F passing through the rotation center Pa (cleaningliquid supplying step). Moreover, the rotation speed of the spin chuck2001 is preferably set in the range of 10 rpm to 1000 rpm.

[0311] At this time, control signals are sent from the controller 2020to the respective electropneumatic regulators 2017 a, 2017 b so that thepressures of air and deionized water are properly adjusted so as to formdroplets at the collision portion G. Simultaneously, the results of thedetections made by the pressure sensors 2018 a, 2018 b and the flow-ratesensors 2019 a, 2019 b, are successively fed back to the controller2020. In other words, the air supplied by the compressed air supplyingsection 2021 is transported through the pipe 2015 a, and the deionizedwater supplied by the deionized water supplying section 2025 issimultaneously transported to the pipe 2015 b.

[0312] At this time, air is discharged from the gas discharging outlet2101 of the cleaning nozzle 2007, and after a lapse of a predeterminedtime, deionized water is supplied from the liquid discharging outlet2201. With this arrangement, the deionized water supplied to thecollision portion G is allowed to form droplets, and simultaneouslymixed with supplied air. Consequently, the deionized water collides withair to be atomized immediately after it has been discharged. Thus, it ispossible to eliminate the wasteful use thereof in the case when it isdischarged onto the surface of the substrate W as the liquid flow. Thesedroplets or mist, as they are, are directly supplied onto the substrateW.

[0313] The discharging speed of the atomized cleaning liquid is properlyset by adjusting the flow rates and flow velocities of the deionizedwater and the air that are maintained in a mutually independent state.In this controlling operation, the air and deionized water do notinterfere with each other, and therefore, desired droplets or mist areobtained by desirably controlling the flow rate and flow velocity of theliquid or the gas. Thus, it becomes possible to remove fine particles onthe substrate sufficiently.

[0314] Next, the rotation of the substrate W driven by the spin chuck2001 is stopped. Lastly, when the cleaning nozzle 2007 has arrived atthe supply end position F, control signals are sent from the controller2020 to the electropneumatic regulators 2017 a, 2017 b so that thesupplies of the respective objects are stopped, and the cleaning nozzle2007 is shifted to the stand-by position 2013. At the time of thestoppage of the cleaning operation, with respect to the cleaning nozzle2007, after the deionized water discharge has been stopped, the airdischarge is stopped. Consequently, it is possible to eliminate thewasteful use of the cleaning liquid in which after the cleaning of thesurface of the substrate W by using the atomized cleaning liquid, thecleaning flow is still discharged onto the surface of the substrate W.

[0315] Then, the substrate W is rotated at a high speed to scatter thecleaning liquid adhering to the surface of the substrate W so that thespinning-off process for drying the substrate W is carried out, therebycompleting the sequence of operations (drying step). Lastly, thesubstrate W is carried out from the spin chuck 2001 by the hand of thesubstrate transporting robot, thereby completing the cleaning step bythe substrate processing apparatus on the substrate W. Then, thesubstrate W is inserted in a cassette capable of housing a plurality ofsubstrates W.

[0316] As described above, in accordance with the present invention, thesurface of the substrate is cleaned by using the mist of the cleaningliquid formed by atomizing the liquid with gas in the air. At this time,the atomized cleaning liquid is generated after the gas and liquid havebeen discharged from the gas discharging means and the liquiddischarging means. For this reason, the flow rates and flow velocitiesof the liquid and gas are maintained in a mutually independent state.Then, the discharged liquid and gas are mixed in the air, and allowed toform an atomized state. Consequently, a desired flow of droplets or mistcurrent is obtained without making the respective flows interfere witheach other upon forming the atomized cleaning liquid. Therefore, it ispossible to sufficiently remove fine particles on the surface of thesubstrate, and consequently to improve the cleaning power exerted on thesurface of the substrate.

[0317] In the above-mentioned embodiments, the center axis P1 passingthrough the gas discharging outlet 2101 of the cleaning nozzle 2007 isdirected perpendicularly to the surface of the substrate W. However,this may be directed diagonally to the surface thereof.

[0318] The mixing operation of a liquid and gas can be attained withanother structure described bellow:

[0319] <2. Second Preferred Embodiment>

[0320]FIG. 16 is a cross-sectional view taken from the apparatus sidethat shows another schematic construction of a cleaning nozzle inaccordance with another preferred embodiment. Here, with respect tomembers that are the same as those of the first preferred embodiment,they are indicated by the same reference numerals, and the descriptionthereof is omitted. A cleaning nozzle 2071 has a trunk portion 2071 bthrough which a gas discharging nozzle 2100 having a gas dischargingoutlet 2101 is inserted. Then, a gas discharging outlet 2101 is formedin the upper surface portion 2071 d of a beveled portion 2071 c of thecleaning nozzle 2007. A liquid outlet nozzle 2300 is placed on the lowerend of the bevel portion 2071 c.

[0321] The liquid discharging nozzle 2300 is arranged in parallel withthe discharging surface 2007 a with its tip being extended in adischarged flow of air below the gas discharging outlet 2101. The tipportion is bent downward so as to allow the liquid discharging outlet2301 to face the surface of the substrate W. Moreover, the center axisline P1 passing through the gas discharging outlet 2101 perpendicularlycrosses the surface of the substrate W, and is also coincident with thecenter axis line passing through the liquid discharging outlet 2301.Thus, the discharged deionized water is smoothly formed into droplets bya discharged flow of air on the periphery thereof, in the proximity ofthe liquid discharging outlet 2301 in the discharging direction.Therefore, the position G1 in the FIG. 16 is a collision portion definedin a open space that is a mixing area between the liquid and the gas. Inother words, in the second preferred embodiment, an arrangement is madeso that the incident angles of the center axis line P1 and the centeraxis line passing through the liquid discharging outlet 2301 are set to0 degree.

[0322] As described above, in the second preferred embodiment, dropletsare smoothly generated by discharging deionized water into thedischarged flow of air. Moreover, since the droplets or mist are formedin the discharged flow, the arrangement is less susceptible toscattering of the droplets, and consequently has a superior cleaningeffect. Here, in the second preferred embodiment, any arrangement may beadopted as long as, into one of the discharged flows, the other isdischarged, and the center axes of the liquid discharging outlet 2301and the gas discharging outlet 2101 are not necessarily coincident witheach other. In other words, the discharging outlet within the dischargedflow may be slightly tilted as long as, into one of the dischargedflows, the other is discharged.

[0323] <3. Modifications>

[0324] The present invention may be modified as described below.

[0325] (1) In the above-mentioned preferred embodiment, air is suppliedfrom the pipe 2015 a, and deionized water is supplied from the pipe 2015b. However, deionized water may be supplied from the pipe 2015 a, andair may be supplied from the pipe 2015 b.

[0326] (2) Moreover, in the above-mentioned one aspect, with respect tothe gas supplied from the pipe 2015 a, only air is use. Alternatively, amixed gas of air and a gas that improves the cleaning degree when mixedwith air may be used, or a gas that simply improves the cleaning degree,such as ozone gas, carbon dioxide or hydrogen, may be suppliedtherefrom.

[0327] (3) In addition to the soft-type substrate cleaning device, whichsupplies a cleaning liquid from the cleaning nozzle 2007, those of ahard type using the cleaning nozzle 2007 in combination with a brush maybe adopted.

[0328] (4) The cleaning nozzle 2007 may be rocked only once in onedirection within the plane of the substrate W on which the cleaningliquid is supplied, and alternatively, this may be rocked several timeswithin the plane of the substrate W.

[0329] (5) With respect to the spin chuck 2001, a pin-holding type spinchuck in which the substrate W is rotated with its circumferential edgeheld by pins from below and on its end surface may be used, andalternatively, a suction-type spin chuck holding the substrate W bysucking the lower surface thereof may be used.

[0330] (6) Furthermore, the spin chuck 2001 may be prepared as at leastthree roller pins or the like that rotate centered on an axis inparallel with the rotation center Pa of the substrate W while contactingthe circumferential end edge of the substrate W. The spin chuck usingthese roller pins is particularly effective in the case when both of thesurfaces of the substrate W are cleaned, and in the case when thecleaning nozzles 2007 are placed at positions sandwiching the substrateW, it is possible to desirably clean the entire areas of both of thesurfaces of the substrate.

[0331] The present invention is widely applied to the cleaning operationfor various other substrates, such as a glass substrate for a liquidcrystal display, a PDP (Plasma Display Panel) substrate or a glasssubstrate and a ceramic substrate used for a magnetic disk. With respectto the shape of the substrate, not limited to the round substrate of theabove-mentioned one aspect, the present invention is also applied tosquare-shaped substrates having a square shape or a rectangular shape.

[0332] (C. Preferred Embodiments According to Third Aspect of thePresent Invention)

[0333] <1. First Preferred Embodiment of Substrate Processing Apparatus>

[0334] In the following, a first preferred embodiment of the substrateprocessing apparatus according to the present aspect will be described.

[0335]FIGS. 17 and 18 show a configuration of a substrate processingapparatus 3001. FIG. 18 is a section view along the line F17-F17 of FIG.17, in which hatching is partially omitted for convenience.

[0336] The substrate processing apparatus 3001 has a cup 3003 of roughlyU shape in cross section as shown in FIG. 17, and roughly ring shapehaving an opening in its center part when viewed from the top surface asshown in FIG. 18; a holding and rotating portion 3005 provided in thevertical direction so as to stand via the opening of the cup 3003, forholding and rotating a substrate W; a remover liquid nozzle 3007 forsupplying the substrate W held by the holding and rotating portion 3005with a remover liquid; and a deionized water nozzle 3009 for similarlysupplying the substrate W held by the holding and rotating portion 3005with deionized water. Also the substrate processing apparatus 3001 has aback surface cleaning nozzle 3011 for supplying the back surface of thesubstrate W held by the holding and rotating portion 3005 with deionizedwater.

[0337] The remover liquid nozzle 3007 constitutes the remover liquidsupplying portion, and the deionized water nozzle 3009 constitutes thedeionized water supplying portion.

[0338] The cup 3003 has a plurality of discharge ports 3004 in itsbottom part. The excess part of the liquid that has been supplied to thesubstrate W reaches to the discharge ports 3004 along the inner wall ofthe cup 3003, and is discharged outside the apparatus via the dischargeports 3004.

[0339] The holding and rotating portion 3005 has a spin motor 3013having a driving shaft which is fixed to the apparatus frame andarranged in the vertical direction, a spin shaft 3014 fixed to thedriving shaft of the spin motor and a vacuum chuck 3015 provided on thetop of the spin shaft 3014 and functioning as a substrate holdingmember.

[0340] The vacuum chuck 3015 has an adsorptive surface for adsorbing thesubstrate on its top surface, the adsorptive surface being smaller inarea than the substrate W when views from the top surface. In thepresent preferred embodiment, the vacuum chuck is a roughly cylindricalmember and the adsorptive surface of the top surface is circular.

[0341] The vacuum chuck 3015 has an adsorptive holes in the adsorptivesurface of the top surface, and adsorbs air through the adsorptiveholes. Thus, the substrate W placed on the vacuum chuck 3015 is held bythe air adsorption through the adsorptive holes. In this way, the vacuumchuck 3015 holds the substrate W while contacting only with the backsurface of the substrate W.

[0342] In the holding and rotating portion 3005 as described above, thesubstrate W placed on the vacuum chuck 3015 is held by adsorption by thevacuum chuck 3015, and the substrate W held on the vacuum chuck 3014 isrotated about an axis 3071 as its center of rotation by driving the spinmotor 3013.

[0343] The remover liquid nozzle 3007 has a first pivot motor 3017having a driving shaft which is fixed to the apparatus frame andarranged in the vertical direction, a first pivot shaft 3019 fixed tothe driving shaft of the first pivot motor 3017, and a first arm 3021connected with the top of the first pivot shaft 3019.

[0344] At the distal end of the first arm 3021 is provided a removerliquid nozzle body 3023.

[0345] The remover liquid nozzle body 3023 constitutes the removerliquid discharge means. The remover liquid nozzle body 3023 is providewith a first through hole 3029, and a first tube 3027 is connected tothe first through hole 3029.

[0346] The first through hole 3029 is a conduit run whose one end isconnected to the first tube 3027 and other end has an opening toward thetop surface of the substrate W. The longitudinal direction of the firstthrough hole 3029 forms a predetermined angle of inclination withrespect to the top surface of the substrate W. This angle of inclinationdetermines an angle of incidence with respect to the top major surfaceof the substrate W of the remover liquid discharged from the firstthrough hole 3029. That is, the angle of inclination of the firstthrough hole 3029 is nearly equal to the angle of incidence with respectto the substrate W of the remover liquid discharged from the firstthrough hole 3029.

[0347] In the present preferred embodiment, since the angle ofinclination of the first through hole 3029 is set at 45 degrees, theremover liquid discharged from the first through hole 3029 reaches thesubstrate W at an angle of incident of 45 degrees.

[0348] On the other hand, the remover liquid nozzle body 3023 isadjusted so that when the first arm 3021 pivots or rotates about an axis3073 in the manner indicated by the arrow 3079, the reach point of aremover liquid 81 discharged from the first through hole 3029 withrespect to the substrate W (hereinafter, referred to as a remover liquidreach point) moves along the line that passes the center of rotation Cof the substrate W and a rotation circle 3095 drawn by the end edge ofthe rotating substrate W.

[0349] In the present preferred embodiment, as shown by the arrow 3085in FIG. 18, it is so adjusted that the remover liquid reach point movesreciprocally on the circular arc that passes the center of rotation C ofthe substrate W and crosses at two points on the circumference of therotation circle 3095. Consequently, the major surface of the substrate Wis scanned with the remover liquid reach point along the arc path.

[0350] The line passing the center of rotation C of the substrate W andthe circumference of the rotation circle 3095 drawn by the end edge ofthe rotating substrate W may be a straight line or a curved line.

[0351] Furthermore, the remover liquid nozzle body 3023 may be moved sothat the remover liquid reach point reciprocally moves on the circulararc whose chord is the radius of the rotation circle 3095 orreciprocally moves on the radius of the rotation circle 3095, orreciprocally moves on the diameter of the rotation circle 3095.

[0352] The line passing the center of rotation C of the substrate W andpassing the circumference of the rotation circle 3095 drawn by the endedge of the rotating substrate W may be a straight line or a curvedline.

[0353] Furthermore, in the first through hole 3029, a first vibrator3025 is provided at the position where it will contact with the removerliquid passing through the first through hole 3029.

[0354] The first tube 3027 supplies the first through hole 3029 with theremover liquid. The first vibrator 3025 vibrates in response to anelectric signal from an oscillator 3067 that will be described below,and applies an ultrasonic wave to the remover liquid passing through thefirst through hole 3029.

[0355] In the remover liquid nozzle 3007 as described above, the firstpivot motor 3017 pivots the first pivot shaft 3019, whereby the firstarm 3021 pivots or rotates about the axis 3073. As a result, as shown inFIG. 18, the remover liquid reach point reciprocally moves on thesubstrate W along the circular arc as shown by the arrow 3085 whilepassing the center of rotation C of the substrate W. Then, the substrateW is supplied with the remover liquid to which an ultrasonic wave hasbeen applied.

[0356] The angle of inclination of the first through hole 3029 from thetop major surface of the substrate may be any angles smaller than 90degrees, with an angle of 30 degrees or more and 60 degrees or lessbeing preferred, with an angle of 45 degrees being most preferred.

[0357] This enables the remover liquid to reach the interface betweenthe reaction products and the surface of the substrate W in thecondition that it is unlikely to be affected by projections anddepressions such as patterns on the substrate W. In other words, theremover liquid can reach the interface between the reaction products andthe surface of the substrate W in the condition that attenuation ofultrasonic wave energy of the remover liquid is small.

[0358] Since the ultrasonic wave oscillates along the dischargedirection of the remover liquid, the remover liquid having reached theinterface between the surface of the substrate W and the reactionproducts have plenty of energy that is effective to enter between thereaction products and the substrate W. Therefore, since the removerliquid strongly acts on the lower part of the reaction products, thereaction products are easily removed from the substrate W and theremoving efficiency is improved.

[0359] In addition, since the remover liquid nozzle body 3023 having thefirst through hole 3029 as described above is adjusted to move so thatthe reach point of the remover liquid moves on the line passing thecenter of rotation C of the substrate W and the circumference of therotation circle 3095 drawn by the end edge of the rotating substrate W,the remover liquid having an ultrasonic wave uniformly applied theretois supplied on the substrate W. Consequently, it is possible to securethe uniformity in the surface of the substrate during process whileimproving the removing efficiency of the reaction products.

[0360] The deionized water nozzle 3009 has a second pivot motor 3031having a driving shaft which is fixed to the apparatus frame andarranged in the vertical direction, a second pivot shaft 3033 fixed tothe driving shaft of the second pivot motor 3031, and a second arm 3035connected with the top of the second pivot shaft 3033.

[0361] The second pivot motor 3031, the second pivot shaft 3033 and thesecond arm 3035 constitute the second movement means.

[0362] At the distal end of the second arm 3035 is provided a deionizedwater nozzle body 3037. The deionized water nozzle body 3037 constitutesthe deionized water discharge means.

[0363] The deionized water nozzle body 3037 is provided with a secondthrough hole 3043 so that the axial direction of the deionized waterdischarged from the second through hole 3043 is directed to the topsurface of the substrate W, and a second tube 3041 is connected to thesecond through hole 3043.

[0364] The second through hole 3043 is a conduit run whose one end isconnected to the second tube 3041 and other end has an opening towardthe top surface of the substrate W. The longitudinal direction of thesecond through hole 3043 forms a predetermined angle of inclination withrespect to the top surface of the substrate W. This angle of inclinationdetermines an angle of incidence with respect to the substrate W of thedeionized water discharged from the second through hole 3043. That is,the angle of inclination of the second through hole 3043 is nearly equalto the angle of incidence with respect to the substrate W of thedeionized water discharged from the second through hole 3043.

[0365] In the present preferred embodiment, since the angle ofinclination of the second through hole 3043 from the top major surfaceof the substrate is set at 45 degrees, the deionized water dischargedfrom the second through hole 3043 reaches the substrate W at an angle ofincident of 45 degrees.

[0366] On the other hand, the deionized water nozzle body 3037 isadjusted so that when the second arm 3035 pivots about an axis 3075 inthe manner indicated by the arrow 3077, the reach point of a deionizedwater 3083 discharged from the second through hole 3043 with respect tothe substrate W (hereinafter, referred to as a deionized water reachpoint) moves on the line that passes the center of rotation C of thesubstrate W and a rotation circle 3095 drawn by the end edge of therotating substrate W.

[0367] In the present preferred embodiment, as shown by the arrow 3087in FIG. 18, it is so adjusted that the deionized water reach point movesreciprocally on the circular arc that passes the center of rotation C ofthe substrate W and crosses at two points on the circumference of therotation circle 3095. Consequently, the major surface of the substrate Wis scanned with the deionized water reach point along the arc path.

[0368] The line passing the center of rotation C of the substrate W andthe circumference of the rotation circle 3095 drawn by the end edge ofthe rotating substrate W may be a straight line or a curved line.

[0369] The deionized water nozzle body 3037 may be moved so that thedeionized water reach point reciprocally moves on the circular arc whosechord is the radius of the rotation circle 3095 or reciprocally moves onthe radius of the rotation circle 3095, or reciprocally moves on thediameter of the rotation circle 3095.

[0370] Furthermore, in the second through hole 3043, a second vibrator3039 is provided at the position where it will contact with thedeionized water passing through the second through hole 3043.

[0371] The second tube 3041 supplies the second through hole 3043 withthe deionized water. The second vibrator 3039 vibrates in response to anelectric signal from an oscillator 3067 that will be described below,and applies an ultrasonic wave to the deionized water passing throughthe second through hole 3043.

[0372] In the deionized water nozzle 3009 as described above, the secondpivot motor 3031 pivots the second pivot shaft 3033, whereby the secondarm 3035 pivots about the axis 3075. As a result, as shown in FIG. 18,the deionized water reach point reciprocally moves on the substrate Walong a circular arc as shown by the arrow 3087 while passing the centerof rotation C of the substrate W. Then, the substrate W is supplied withthe deionized water to which an ultrasonic wave has been applied.

[0373] The angle of inclination of the second through hole 3043 from thetop major surface of the substrate may be any angles smaller than 90degrees, with an angle of 30 degrees or more and 60 degrees or lessbeing preferred, with an angle of 45 degrees being most preferred.

[0374] This enables the deionized water to reach the interface betweenthe reaction products and the surface of the substrate W in thecondition that it is unlikely to be affected by projections anddepressions such as patterns on the substrate W. In other words, thedeionized water can reach the interface between the reaction productsand the surface of the substrate W in the condition that attenuation ofultrasonic wave energy of the deionized water is small.

[0375] Since the ultrasonic wave oscillates along the dischargedirection of the deionized water, the deionized water having reached theinterface between the surface of the substrate W and the reactionproducts has plenty of energy that is effective to cut in between thereaction products and the substrate W. Therefore, since the deionizedwater strongly acts on the lower part of the reaction products, thereaction products are easily removed from the substrate W and theremoving efficiency is improved.

[0376] In addition, since the deionized water nozzle body 3037 havingthe second through hole 3043 as described above is adjusted to move sothat the reach point of the deionized water moves on the line passingthe center of rotation C of the substrate W and the circumference of therotation circle 3095 drawn by the end edge of the rotating substrate W,the deionized water having an ultrasonic wave uniformly applied theretois supplied on the substrate W. Consequently, it is possible to securethe uniformity in the surface of the substrate during process whileimproving the removing efficiency of the reaction products.

[0377] The back surface cleaning nozzle 3011 is a tubular member whichpenetrates through the cup 3003 and extends in the roughly verticaldirection toward the back surface of the substrate W, and supplied withdeionized water via a back surface cleaning valve 3065 as will bedescribed below. As a result, it is possible to discharge deionizedwater with respect to the back surface of the substrate W.

[0378] Next, a remover liquid supplying system for the remover liquidnozzle 3007 and a deionized water supplying system 3091 for thedeionized water nozzle 3009 and the back surface nozzle 3011 will beexplained with reference to FIG. 19.

[0379] A remover liquid supplying system 3089 has a remover liquid pump3047 for pumping remover liquid from a remover liquid source 3045provided outside the apparatus, a temperature controller 3051 forcontrolling the temperature of the remover liquid by heating or coolingthe remover liquid pumped by the remover liquid pump 3047 to apredetermined temperature, a filter 3049 for filtering contaminants fromthe remover liquid whose temperature has been controlled by thetemperature controller 3051, and a remover liquid nozzle valve 53 foropening/closing passage of the remover liquid after being subjected tothe filtering toward the remover liquid nozzle 3007.

[0380] With the configuration as described above, the remover liquidsupplying system 3089 can supply the remover liquid nozzle 3007 with theremover liquid whose temperature has been controlled to thepredetermined temperature by means of the temperature controller 3051and which has been cleaned by means of the filter 3049.

[0381] The deionized water supplying system 3091 has a deionized waterpump 3057 for pumping deionized water from a deionized water source 3055provided outside the apparatus, a temperature controller 3061 forcontrolling the temperature of the deionized water by heating or coolingthe deionized water pumped by the deionized water pump 3057 to apredetermine temperature, a filter 3059 for filtering contaminants fromthe deionized water whose temperature has been controlled by thetemperature controller 3061, a deionized water nozzle valve 3063 foropening/closing passage of the deionized water after being subjected tothe filtering toward the deionized water nozzle 3009, and the backsurface cleaning valve 3065 for opening/closing passage of the deionizedwater after being subjected to the filtering toward the back surfacecleaning nozzle.

[0382] With the configuration as described above, the deionized watersupplying system 3091 can supply the deionized water nozzle 3009 withthe deionized water whose temperature has been controlled to thepredetermined temperature by means of the temperature controller 3061and which has been cleaned by means of the filter 3059.

[0383] Next, an ultrasonic wave applying portion 3093 will be explainedwith reference to FIG. 19 again.

[0384] The ultrasonic wave applying portion 3093 has the first vibrator3025 provided within the remover liquid nozzle 3007 and the oscillator3067 for transmitting an electric signal to the first vibrator 3025 tocause the first vibrator 3025 to vibrate.

[0385] With such a configuration, the ultrasonic wave applying portion3093 applies an ultrasonic wave to the remover liquid that is to besupplied to the substrate W from the remover liquid nozzle 3007.

[0386] In addition, the ultrasonic wave applying portion 3093 has thesecond vibrator 3039 provided within the deionized water nozzle 3009 andthe second vibrator 3039 vibrates in response to an electric signaltransmitted from the oscillator 3067.

[0387] With such a configuration, the ultrasonic wave applying portion3093 applies an ultrasonic wave to the deionized water that is to besupplied to the substrate W from the deionized water nozzle 3009.

[0388] As described above, since the substrate W can be supplied withthe remover liquid or deionized water to which ultrasonic wave has beenapplies, it is possible to remove the reaction products more quickly andhence the throughput is improved. Though the throughput is improved byapplying an ultrasonic wave to either one of the remover liquid or thedeionized water, it is possible to remove the reaction products morequickly and improve the throughput by applying ultrasonic waves to bothof the remover liquid and the deionized water.

[0389] Next, a hard configuration of the substrate processing apparatus3001 will be explained with reference to FIG. 20.

[0390] To a control means 3069, connected are the spin motor 3013, thefirst pivot motor 3017, the second pivot motor 3031, the oscillator3067, the remover liquid pump 3047, the deionized water pump 3057, theremover liquid nozzle valve 3053, the deionized water nozzle valve 3063,the back surface cleaning valve 3065, the temperature controller 3051and the temperature controller 3061, and the control means 3069 controlsthese connected members in the manner as described in the first andsecond preferred embodiments of the substrate processing method thatwill be described below.

[0391] Though the substrate processing apparatus 3001 of the presentpreferred embodiment has both of the first vibrator 3025 for applying anultrasonic wave to the remover liquid and the second vibrator 3039 forapplying an ultrasonic wave to the deionized water, it is also possibleto have either one of these vibrators.

[0392] <2. First Preferred Embodiment of Substrate Processing Method>

[0393]FIG. 21 is a view showing the first preferred embodiment of thesubstrate processing method using the above-described substrateprocessing apparatus 3001. As shown in FIG. 21, the substrate processingmethod of the present preferred embodiment comprises a remover liquidsupplying step s3001, a remover liquid dispersing step s3002, adeionized water supplying step s3003 and a deionized water dispersingstep s3004. In the following, each step will be explained with referenceto FIG. 22.

[0394] (1. Remover Liquid Supplying Step s3001)

[0395] First, until the time t3000, the control means 3069 controls thetemperature controllers 3051 and 3061 so that the remover liquid and thedeionized water have predetermined temperatures.

[0396] On the other hand, until the time t3000, the control means 3069drives the spin motor 3013 to rotate the substrate W, so that thesubstrate W rotates at a predetermined rotation speed at the time t3000.

[0397] Then, at the time t3000, the control means 3069 controls thefirst pivot motor 3017 to pivot, thereby controlling the remover liquidnozzle 3007 to swivel.

[0398] Furthermore, at the time t3000, the control means 3069 drives theremover liquid pump 3047, thereby allowing the remover liquid to bedischarged toward the remover liquid nozzle 3007, while switching theremover liquid nozzle valve 3053 to an open state, thereby making theremover liquid nozzle 3007 supply the remover liquid to the substrate W.As a consequence, the remover liquid supplied from the remover liquidnozzle 3007 is supplied on the substrate W so that the reach point tothe substrate W moves on the circular arc passing the center of rotationC of the substrate W in the horizontal surface including the surface ofthe substrate W as shown by the arrow 3085 in FIG. 18. In this way, theremover liquid supplying step s3001 is executed.

[0399] On the other hand, at the time t3000, the control means 3069controls the oscillator 3067 to transmit an electric signal to the firstvibrator 3025 within the remover liquid nozzle 3007, thereby making thefirst vibrator 3025 vibrate. As a consequence, an ultrasonic wave isapplied to the remover liquid to be supplied from the remover liquidnozzle 3007. Therefore, ultrasonic vibration is applied to the reactionproducts adhered to the substrate W, so that the reaction productsbecome easy to be removed from the substrate W.

[0400] At the time t3001 after a predetermined time period has elapsed,the control means 3069 stops driving of the first pivot motor 3017 inthe condition that the remover liquid nozzle 3007 is retracted fromabove the cup 3003. Furthermore, the control means 3069 switches theremover liquid nozzle valve 3053 to a closed state, and stops driving ofthe remover liquid pump 3047, thereby stopping supply of the removerliquid from the remover liquid nozzle 3007. The control means 3069causes the oscillator 3067 to stop transmission of an electric signal tothe first vibrator 3025 at the time t3001.

[0401] By making the reach point of the remover liquid move on thecircular arc passing the center of rotation C of the substrate W asdescribed above, it is possible to supply the entire substrate W with aremover liquid which is small in temperature change and is notdeteriorated and hence fresh, making it possible to easily remove thereaction products and secure the uniformity in the surface in the entiresubstrate W.

[0402] (2. Remover Liquid Dispersing Step s3002)

[0403] Next, at the time t3001, the control means 3069 stops supply ofthe remover liquid to the substrate W, while controlling the spin motor3013 to continuously rotate, thereby maintaining the rotating state ofthe substrate W. As a consequence, the remover liquid dispersing steps3002 is executed.

[0404] In this remover liquid dispersing step s3002, the substrate W isrotated at a rotation speed of 500 rpm or more, preferably at a rotationspeed in the range of 1000 rpm to 4000 rpm.

[0405] Furthermore, the time that the rotation is maintained is at least1 second or more, preferably 2 to 5 seconds.

[0406] In this way, since the rotating state of the substrate ismaintained in the condition that supply of the remover liquid to thesubstrate W is stopped, the remover liquid on the substrate W isdispersed from the substrate W owing to the centrifugal force.

[0407] Since the substrate is rotated while being held in the horizontalstate, the remover liquid is dispersed uniformly from the substrate W.Therefore, the uniformity in the surface of the substrate W ismaintained.

[0408] Furthermore, since the vacuum chuck 3015 contacts only with theback surface of the substrate W, there is no member that contacts withthe end edge of the substrate W. Therefore, there is no object thatprevents advance of the remover liquid dispersed from the top surface ofthe substrate W to outside of the substrate W in the horizontaldirection, so that the time required for dispersing the remover liquidfrom the substrate W is reduced. Accordingly, it is possible to improvethe throughput.

[0409] Since the holding and rotating portion 3005 merely holds onesubstrate W, the rotation speed of the substrate W can be easilyincreased. As a result, the time period required for dispersing theremover liquid from the substrate W is reduced. This is also effectiveto improve the throughput.

[0410] (3. Deionized Water Supplying Step s3003)

[0411] At the time t3002, the control means 3069 controls the secondpivot motor 3032 to pivot, thereby controlling the deionized waternozzle 3009 to swivel.

[0412] At time t3002, the control means 3069 drives the deionized waterpump 3057, thereby allowing the deionized water to be discharged towardthe deionized water nozzle 3009, while switching the deionized waternozzle valve 3063 to an open state, thereby making the deionized waternozzle 3009 supply the deionized water to the substrate W. As aconsequence, the deionized water supplied from the deionized waternozzle 3009 is supplied on the substrate W so that the reach point tothe substrate W moves on the circular arc passing the center of rotationC of the substrate W in the horizontal surface including the surface ofthe substrate W as shown by the arrow 3087 in FIG. 18. In this way, thedeionized water supplying step s3003 is executed.

[0413] On the other hand, at the time t3002, the control means 3069controls the oscillator 3067 to transmit an electric signal to thesecond vibrator 3039 within the deionized water nozzle 3009, therebymaking the second vibrator 3039 vibrate. As a consequence, an ultrasonicwave is applied to the deionized water to be supplied from the deionizedwater nozzle 3009. Therefore, ultrasonic vibration is applied to thereaction products adhered to the substrate W, so that the reactionproducts become easy to be removed from the substrate W.

[0414] Also, at the time t3002, the control means 3069 switches the backsurface cleaning valve 3065 to an opened state to make the back surfacecleaning nozzle 3011 supply deionized water to the back surface of thesubstrate W, thereby cleaning the back surface of the substrate W.

[0415] At the time t3003 after a predetermined time period has elapsed,the control means 3069 stops driving of the second pivot motor 3031 inthe condition that the deionized water nozzle 3009 is retracted fromabove the cup 3003. The control means 3069 switches the deionized waternozzle valve 3063 to a closed state, and stops driving of the deionizedwater pump 3057, thereby stopping supply of the deionized water from thedeionized water nozzle 3009. The control means 3069 causes theoscillator 3067 to stop transmission of the electric signal to thesecond vibrator 3039 at the time t3003.

[0416] By making the reach point of the deionized water move on thecircular arc passing the center of rotation C of the substrate W asdescribed above, it is possible to supply the entire substrate W withdeionized water which is small in temperature change and is notdeteriorated and hence fresh, making it possible to easily remove thereaction products and secure the uniformity in the surface in the entiresubstrate W.

[0417] (2. Deionized Water Dispersing Step s3004)

[0418] At the time t3003, the control means 3069 stops supply of thedeionized water to the substrate W, while controlling the spin motor3013 to continuously rotate, thereby maintaining the rotating state ofthe substrate W. As a consequence, the deionized water dispersing steps3004 is executed.

[0419] The reaction products are removed by the remover liquid and thedeionized water supplied to the substrate W in the manner as describedabove.

[0420] According to the present preferred embodiment, in the removerliquid dispersing step s3002, the remover liquid on the substrate W isdispersed, so that no or very few remover liquid remains on thesubstrate W. Therefore, even if the substrate W is supplied with thedeionized water in the deionized water supplying step s3003 under thiscondition, no or a small amount of remover liquid becomes contact withthe deionized water, so that a pH shock, if it occurs, will hardlyaffect on the substrate W, or such a pH shock itself does not occur.Therefore, the necessity of the intermediate rinse step is eliminated,and hence the throughput is improved. Furthermore, by omitting theintermediate rinse step, it is possible to reduce the cost and eliminatethe necessity of using an organic solvent used in the intermediate rinsestep, resulting in improvement of the safety of the apparatus.

[0421] Furthermore, since the remover liquid and the deionized water towhich an ultrasonic wave is supplied are supplied, it is possible toremove the reaction products more quickly.

[0422] While rotation of the substrate W is not stopped from start ofthe remover liquid supplying step s3001 until end of the deionized waterdispersing step s3004 in the substrate processing method of the presentpreferred embodiment, rotation of the substrate W may be stopped eitherbetween the remover liquid supplying step s3001 and the remover liquiddispersing step s3002, between the remover liquid dispersing step s3002and the deionized water supplying step s3003, or between the deionizedwater supplying step s3003 and the deionized water dispersing steps3004.

[0423] It is essential to provide a step of stopping rotation of thesubstrate W for reducing the remover liquid on the substrate W even inshort time before staring the deionized water supplying step s3003.

[0424] Rotation speeds of the substrate W in the remover liquidsupplying step s3001, the remover liquid dispersing step s3002, thedeionized water supplying step s3003 and the deionized water dispersingstep s3004 may be equal to each other or different from each other.

[0425] While an ultrasonic wave is applied to both the remover liquidand the deionized water in the substrate processing method of thepresent preferred embodiment, the ultrasonic wave may be applied toeither one of the remover liquid or the deionized water.

[0426] <3. Second Preferred Embodiment of Substrate Processing Method>

[0427] A substrate processing method of the second preferred embodimentwill be described with reference to FIG. 23.

[0428] The substrate processing method of the second preferredembodiment repeats the substrate processing method of the firstpreferred embodiment twice.

[0429] That is, the substrate processing method of the present preferredembodiment comprises: a first remover liquid supplying step s3011; afirst remover liquid dispersing step s3012; a first deionized watersupplying step s3013; a first deionized water dispersing step s3014; asecond remover liquid supplying step s3021; a second remover liquiddispersing step s3022; a second deionized water supplying step s3023;and a second deionized water dispersing step s3024.

[0430] In this context, the first remover liquid supplying step s3011and the second remover liquid supplying step s3022 are as same as theremover liquid supplying step s3001 in the first preferred embodiment ofthe substrate processing method.

[0431] Furthermore, the first remover liquid dispersing step s3012 andthe second remover liquid dispersing step s3022 are as same as theremover liquid dispersing step s3002 in the first preferred embodimentof the substrate processing method.

[0432] Furthermore, the first deionized water supplying step s3013 andthe second deionized water supplying step s3023 are as same as thedeionized water supplying step s3003 in the first preferred embodimentof the substrate processing method.

[0433] Furthermore, the first deionized water dispersing step s3014 andthe second deionized water dispersing step s3024 are as same as thedeionized water dispersing step s3004 in the first preferred embodimentof the substrate processing method.

[0434] In this substrate processing method of the second preferredembodiment, there is the first deionized water dispersing step s3014between the first deionized water supplying step s3013 and the secondremover liquid supplying step s3021. Therefore, the deionized watersupplied on the substrate W in the first deionized water supplying steps3013 is dispersed in the first deionized water dispersing step s3014 sothat little or no deionized water remains on the substrate W. If thesubstrate W is supplied with the remover liquid under this condition, asmall amount of or no deionized water will come into contact with theremover liquid, so that a pH shock will hardly affect on the substrate Wor a pH shock itself will not occur.

[0435] While the present preferred embodiment repeats the substrateprocessing method of the first preferred embodiment twice, the number ofrepetition may be repeated more than two.

[0436] <4. Second Preferred Embodiment of Substrate ProcessingApparatus>

[0437] The second preferred embodiment of the substrate processingapparatus of the present invention will be explained with reference toFIGS. 24 and 25.

[0438]FIG. 24 is a cross section viewed in the direction of F24-F24 ofFIG. 25, in which hatching is partially omitted for convenience.

[0439] A substrate processing apparatus 3100 of the second preferredembodiment has a solvent nozzle 3002 serving as an intermediate rinseliquid supplying portion in addition to the substrate processingapparatus 3001 of the first preferred embodiment. The solvent nozzle3002 constitutes the intermediate rinse liquid supplying portion.

[0440] Since the substrate processing apparatus 3100 of the secondpreferred embodiment has many equivalent parts with the substrateprocessing apparatus 3001 of the first preferred embodiment, the partequivalent to that of the substrate processing apparatus 3001 will bedenoted by the same reference numeral in the drawing and explanationthereof will be omitted.

[0441] As shown in FIG. 24, the substrate processing apparatus 3100 hasthe solvent nozzle 3002.

[0442] The solvent nozzle 3002 has a third pivot motor 3018 having adriving shaft which is fixed to the apparatus frame and arranged in thevertical direction, a third pivot shaft 3020 fixed to the driving shaftof the third pivot motor 3018, and a third arm 3022 connected with thetop of the third pivot shaft 3020.

[0443] The third pivot motor 3018, the third pivot shaft 3020 and thethird arm 3022 constitute the third movement means.

[0444] At the distal end of the third arm 3022 is provided a solventnozzle body 3024. The solvent nozzle body 3024 constitutes theintermediate rinse liquid discharge means.

[0445] The solvent nozzle body 3024 is provide with a third through hole3030 so that the axial direction of the solvent to be discharged fromthe third through hole 3030 is directed to the top surface of thesubstrate W, and a third tube 28 is connected to the third through hole3030.

[0446] The third through hole 3030 is a conduit run whose one end isconnected to the third tube 3028 and other end has an opening toward thetop surface of the substrate W. The longitudinal direction of the thirdthrough hole 3030 forms a predetermined angle of inclination withrespect to the top surface of the substrate W. This angle of inclinationdetermines an angle of incidence with respect to the substrate W of theorganic solvent discharged from the third through hole 3030. That is,the angle of inclination of the third through hole 3030 is nearly equalto the angle of incidence with respect to the substrate W of the removerliquid discharged from the third through hole 3030.

[0447] In the present preferred embodiment, since the angle ofinclination of the third through hole 3030 is set at 45 degrees, theorganic solvent discharged from the third through hole 3030 reaches thesubstrate W at an angle of incident of 45 degrees.

[0448] On the other hand, the solvent nozzle body 3024 is adjusted sothat when the third arm 3022 pivots about an axis 3074 in the mannerindicated by the arrow 3078, the reach point of an organic solvent 3082discharged from the third through hole 3030 with respect to thesubstrate W (hereinafter, referred to as a solvent reach point) moves onthe line that passes the center of rotation C of the substrate W and arotation circle 3095 drawn by the end edge of the rotating substrate W.

[0449] In the present preferred embodiment, as shown by the arrow 3086in FIG. 25, it is so adjusted that the deionized water reach point movesreciprocally on the circular arc that passes the center of rotation C ofthe substrate W and crosses at two points on the circumference of therotation circle 3095. Consequently, the major surface of the substrate Wis scanned with the reach a solvent reach point along the arc path.

[0450] The line passing the center of rotation C of the substrate W andthe circumference of the rotation circle 3095 drawn by the end edge ofthe rotating substrate W may be a straight line or a curved line.

[0451] Furthermore, the solvent nozzle body 3024 may be moved so thatthe deionized water reach point reciprocally moves on the circular arcwhose chord is the radius of the rotation circle 3095 or reciprocallymoves on the radius of the rotation circle 3095, or reciprocally moveson the diameter of the rotation circle 3095.

[0452] In the third through hole 3030, a third vibrator 3026 is formedat the position where it will contact with the organic solvent passingthrough the third through hole 3030.

[0453] The third tube 28 supplies the third through hole 3030 with theorganic solvent. The third vibrator 3026 vibrates in response to anelectric signal from an oscillator 3067, and applies an ultrasonic waveto the organic solvent passing through the third through hole 3030.

[0454] In the solvent nozzle 3002 as described above, the third pivotmotor 3018 rotates the third pivot shaft 3020, whereby the third arm3022 swivels about the axis 3074. As a result, as shown in FIG. 25, thereach point of the organic solvent 3081 reciprocally moves on thesubstrate W along a circular arc as shown by the arrow 3086 whilepassing the center of rotation C of the substrate W. Then, the substrateW is supplied with the organic solvent to which an ultrasonic wave hasbeen applied.

[0455] The angle of inclination of the third through hole 3030 may beany angles smaller than 90 degrees, with an angle of 30 degrees or moreand 60 degrees or less being preferred, with an angle of 45 degreesbeing most preferred.

[0456] This enables the organic solvent to reach the interface betweenthe reaction products and the surface of the substrate W in thecondition that it is unlikely to be affected by projections anddepressions such as patterns on the substrate W. In other words, theorganic solvent can reach the interface between the reaction productsand the surface of the substrate W in the condition that attenuation ofultrasonic wave energy of the organic solvent is small.

[0457] Since the ultrasonic wave oscillates along the dischargedirection of the organic solvent, the organic solvent having reached theinterface between the surface of the substrate W and the reactionproducts have plenty of energy that is effective to cut in between thereaction products and the substrate W. Therefore, since the organicsolvent strongly acts on the lower part of the reaction product, thereaction products are easily removed from the substrate W and theremoving efficiency is improved.

[0458] In addition, since the solvent nozzle body 3024 having the thirdthrough hole 3030 as described above is adjusted to move so that thereach point of the solvent moves on the line passing the center ofrotation C of the substrate W and the circumference of the rotationcircle 3095 drawn by the end edge of the rotating substrate W, theorganic solvent having an ultrasonic wave uniformly applied thereto issupplied on the substrate W. Consequently, it is possible to secure theuniformity in the surface of the substrate during process whileimproving the removing efficiency of the reaction product.

[0459] In addition, since the remover liquid remaining in the vicinityof the interface between the reaction products and the substrate W canalso be cleaned, it is possible to desirably remove the remover liquidfrom the substrate W. Therefore, even if the deionized water is suppliedto the substrate in the deionized water supplying step that will bedescribed below, a pH shock is unlikely to occur.

[0460] The back surface solvent nozzle 3012 is a tubular member whichpenetrates through the cup 3003 and extends in the roughly verticaldirection toward the back surface of the substrate W, and supplied withan organic solvent via a back surface solvent valve 3066 as will bedescribed below. As a result, it is possible to discharge an organicsolvent with respect to the back surface of the substrate W.

[0461]FIG. 26 shows a solvent supplying system 3090 for supplying thesolvent nozzle 3002 with an organic solvent.

[0462] The solvent supplying system 3080 has a solvent pump 3048 forpumping an organic solvent from a solvent source 3046 provided outsidethe apparatus, a temperature controller 3050 for controlling thetemperature of the organic solvent by heating or cooling the organicsolvent pumped by the solvent pump 3048 to a predetermine temperature, afilter 3052 for filtering contaminants from the organic solvent whosetemperature has been controlled by the temperature controller 3050, asolvent nozzle valve 3054 for opening/closing passage of the organicsolvent after being subjected to the filtering toward the solvent nozzle3002, and the back surface solvent valve 3066 for opening/closingpassage of the organic solvent after being subjected to the filteringtoward the back surface solvent nozzle 3012.

[0463] With the configuration as described above, the solvent supplyingsystem 3090 can supply the solvent nozzle 3002 with the organic solventwhose temperature has been controlled to the predetermined temperatureby means of the temperature controller 3052 and which has been cleanedby means of the filter 50.

[0464] In addition, the ultrasonic wave applying portion 3093 has thethird vibrator 3026 provided within the solvent nozzle 3002 and thethird vibrator 3026 vibrates in response to an electric signaltransmitted from the oscillator 3067.

[0465] With such a configuration, the ultrasonic wave applying portion3093 applies an ultrasonic wave to the organic solvent that is to besupplied to the substrate W from the solvent nozzle 3002.

[0466] As described above, since the substrate W can be supplied withthe organic solvent to which ultrasonic wave has been applied, it ispossible to remove the reaction products more quickly and hence thethroughput is improved. Though the throughput is improved by applying anultrasonic wave to either one of the organic solvent or the deionizedwater, it is possible to remove the reaction products more quickly andimprove the throughput by applying an ultrasonic wave to two or all ofthe remover liquid, the organic solvent and the deionized water.

[0467] Next, a hardware configuration of the substrate processingapparatus 3100 will be explained with reference to FIG. 27.

[0468] Similarly to the control means 3069 in the first preferredembodiment of the substrate processing apparatus, to a control means3070, the spin motor 3013, the first pivot motor 3017, the second pivotmotor 3031, the oscillator 3067, the remover liquid pump 3047, thedeionized water pump 3057, the remover liquid nozzle valve 3053, thedeionized water nozzle valve 3063, the back surface cleaning valve 3065,the temperature controller 3051 and the temperature controller 3061 areconnected.

[0469] Furthermore, to the control means 3070, the third pivot motor3018, the solvent pump 3048, the solvent nozzle valve 3054, the backsurface solvent valve 3066 and the temperature controller 3052 areconnected.

[0470] The control means 3070 controls these connected members in themanner as described in the third preferred embodiment of the substrateprocessing method that will be described below.

[0471] Though the substrate processing apparatus 3100 of the presentpreferred embodiment has three vibrators, the first vibrator 3025 forapplying an ultrasonic wave to the remover liquid, the second vibrator3039 for applying an ultrasonic wave to the deionized water and thethird vibrator 3026 for applying an ultrasonic wave to the organicsolvent, it is also possible to have either one or two of thesevibrators.

[0472] <5. Third Preferred Embodiment of Substrate Processing Method>

[0473] Referring to FIG. 28, the third preferred embodiment of thesubstrate processing method using the above-described substrateprocessing apparatus 3100 will be explained.

[0474] The substrate processing method of the present preferredembodiment comprises a remover liquid supplying step s3031, a removerliquid dispersing step s3032, a solvent supplying step s3033 as anintermediate rinse step, a deionized water supplying step s3034 and adeionized water dispersing step s3035.

[0475] Substantially, the substrate processing method of the presentpreferred embodiment is such that a solvent supplying step is appliedbetween the remover liquid dispersing step s3002 and the deionized watersupplying step s3003 in the substrate processing method of the firstpreferred embodiment which comprises the remover liquid supplying steps3001, the remover liquid dispersing step s3002, the deionized watersupplying step s3003 and the deionized water dispersing step s3004.

[0476] Therefore, the remover liquid supplying step s3031, the removerliquid dispersing step s3032, the deionized water supplying step s3034and the deionized water dispersing step s3035 correspond to the removerliquid supplying step s3001, the remover liquid dispersing step s3002,the deionized water supplying step s3003 and the deionized waterdispersing step s3004 in the substrate processing method of the firstpreferred embodiment, respectively, so that the explanations thereofwill be omitted.

[0477] Next, the solvent supplying step s3033 of the present preferredembodiment will be explained. As shown in FIG. 29, after the removerliquid supplying step s3031 and the remover liquid dispersing steps3032, the solvent supplying step s3033 is executed. In the removerliquid dispersing step s3032, since the substrate is kept rotating inthe condition that supplying of the remover liquid to the substrate W isstopped, the remover liquid on the substrate W is dispersed from on thesubstrate W by the centrifugal force, so that the remover liquidremaining on the substrate W becomes as small as possible.

[0478] Next, at time t3002, the control means 3070 controls the thirdpivot motor 3018 to pivot, thereby rotating the solvent nozzle 3002.

[0479] Furthermore, at the time t3002, the control means 3070 drives thesolvent pump 3048, thereby allowing the organic solvent to be dischargedtoward the solvent nozzle 3002, and drives temperature controller 3052to control the organic solvent to a predetermined temperature, whileswitching the solvent nozzle valve 3054 to an open state, thereby makingthe solvent nozzle 3002 supply the organic solvent to the substrate W.As a consequence, the organic solvent supplied from the solvent nozzle3002 is supplied on the substrate W so that the reach point to thesubstrate W moves on the circular arc passing the center of rotation Cof the substrate W in the horizontal surface including the surface ofthe substrate W as shown by the arrow 3086 in FIG. 25. In this way, thesolvent supplying step s3033 is executed.

[0480] On the other hand, at the time t3002, the control means 3070controls the oscillator 3067 to transmit an electric signal to the thirdvibrator 3026 within the solvent nozzle 3002, thereby making the thirdvibrator 3026 vibrate. As a consequence, an ultrasonic wave is appliedto the organic solvent to be supplied from the solvent nozzle 3002.

[0481] For this reason, ultrasonic vibration is applied to the reactionproducts adhered to the substrate W, so that the reaction productsbecome easy to be removed from the substrate W.

[0482] Furthermore, at the time t3002, the control means 3070 switchesthe back surface solvent valve 3066 to the open state to allow the backsurface solvent nozzle 3012 to supply the back surface of the substrateW with the organic solvent, thereby cleaning out the remover liquid onthe back surface of the substrate W.

[0483] As described above, in the solvent supplying step s3033, bysupplying the substrate W with the organic solvent, the remover liquidis completely removed from the substrate W. Consequently, when thesubstrate W is supplied with the deionized water in the subsequentdeionized water supplying step s3034, there is no remover liquid thatwill come into contact with the deionized water, so that it is possibleto prevent a pH shock from occurring. Therefore, it is possible toprevent occurrence of damage to the thin film on the substrate W.

[0484] Moreover, since the remover liquid is dispersed from thesubstrate W in the remover liquid dispersing step s3032 in the presentpreferred embodiment, the remover liquid remaining on the substrate W isslight at this point of time. Therefore, it is possible to reduce thetime required for cleaning out the remover liquid by the organic solventin the solvent supplying step s3033. As a result, the throughput isimproved. Similarly, since the remover liquid remaining on the substrateis slight, it is possible to reduce the amount of organic solventrequired in the solvent supplying step s3033 and reduce the cost.

[0485] In the present preferred embodiment, while the deionized watersupplying step s3034 is executed directly after the solvent supplyingstep s3033, a solvent dispersing step for dispersing the solvent on thesubstrate W may be provided between the solvent supplying step s3033 andthe deionized water supplying step s3034.

[0486] While rotation of the substrate W is not stopped from start ofthe remover liquid supplying step s3031 until end of the deionized waterdispersing step s3035 in the substrate processing method of the presentpreferred embodiment, rotation of the substrate W may be stopped eitherbetween the remover liquid supplying step s3031 and the remover liquiddispersing step s3032, between the remover liquid dispersing step s3032and the solvent supplying step s3033, between the solvent supplying steps3033 and the deionized water supplying step s3034, or between thedeionized water supplying step s3034 and the deionized water dispersingstep s3035.

[0487] It is essential to provide a step of stopping rotation of thesubstrate W and reducing the remover liquid on the substrate W even inshort time before staring the solvent supplying step s3033. This reducesthe time required for the solvent supplying step s3035, improves thethroughput and reduces the cost.

[0488] Furthermore, since the remover liquid, the organic solvent andthe deionized water to which an ultrasonic wave is applied are supplied,it is possible to remove the reaction products more quickly.

[0489] In the present preferred embodiment, a series of process of theremover liquid supplying step s3031, the remover liquid dispersing steps3032, the solvent supplying step s3033, the deionized water supplyingstep s3034 and the deionized water dispersing step s3035 is executedonce, however, this series of process may be repeated for plural times.

[0490] <6. Third Preferred Embodiment of Substrate Processing Apparatus>

[0491] Referring to FIGS. 30 and 31, the third preferred embodiment ofthe substrate processing apparatus of the present aspect will beexplained. FIG. 31 is a top view of FIG. 30.

[0492] A major difference of a substrate processing apparatus 200 of thethird preferred embodiment from the substrate processing apparatus 3001of the first preferred embodiment and the substrate processing apparatus3100 of the second preferred embodiment is that no vibrator for applyingan ultrasonic wave to a process liquid is provided in nozzles whichdischarge such process liquids as a remover liquid, intermediate rinseliquid and deionized water, whereas direct vibration applying means fordirectly applying an ultrasonic wave while being in contact with theprocess liquid discharged onto the substrate and existing on thesubstrate.

[0493] Furthermore, the substrate processing apparatus 200 is differentfrom the substrate processing apparatus 3100 of the second preferredembodiment in that the solvent nozzle body and the deionized waternozzle body are mounted on a single arm, however, other configurationincluding the holding and rotating portion, the remover liquid supplyingsystem, the solvent supplying system and the deionized water supplyingsystem is approximately equal to that of the substrate processingapparatus 3100. Therefore, the following explanation will be made ononly different parts.

[0494] As shown in FIG. 30, the substrate processing apparatus 3200comprises a remover liquid nozzle portion 3207 for supplying thesubstrate W with a remover liquid, a rinse system nozzle portion 3209for supplying the substrate W with an organic solvent and deionizedwater and a direct vibration applying means 3225. Though omitted in thedrawing, the substrate W is held by the holding and rotating portion inthe manner similar to the substrate processing apparatus 3100.

[0495] The remover liquid nozzle portion 3207 has a first pivot motor3217 having a driving shaft fixed to the apparatus frame and arranged inthe vertical direction, a first pivot shaft 3219 fixed to the drivingshaft of the first pivot motor 3217 and a first arm 3221 connected tothe top portion of the first pivot shaft 3219.

[0496] At the distal end of the first arm 3221 is provided a firstfixing block 3229, and the first fixing block 3229 is provided with aremover liquid nozzle body 3223.

[0497] The remover liquid nozzle body 3223 is a tubular member arrangedin the vertical direction, of which one end has an opening toward thesubstrate W and other end is supplied with the remover liquid from theremover liquid supplying system. In this way, the remover liquid nozzlebody 3223 discharges the remover liquid to the substrate W.

[0498] In the present preferred embodiment, as shown by the arrow 3285of FIG. 31, the remover liquid nozzle body 3223 is moved so that thereach point of the remover liquid with respect to the substrate W moveson the circular arc whose chord is the radius of the rotation circle3095 drawn by the rotating end edge of the substrate W.

[0499] The rinse system nozzle portion 3209 has a second pivot motor3231 having a driving shaft fixed to the apparatus frame and arranged inthe vertical direction, a second pivot shaft 3233 fixed to the drivingshaft of the second pivot motor 3231 and a second arm 3235 connected tothe top portion of the second pivot shaft 3233.

[0500] At the distal end of the second arm 3235 is provided a secondfixing block 3243, and the second fixing block 3243 is provided with adeionized water nozzle body 3237 and a solvent nozzle body 3224.

[0501] The deionized water nozzle body 3237 is a tubular member arrangedin the vertical direction, of which one end has an opening toward thesubstrate W and other end is supplied with deionized water from thedeionized water supplying system. In this way, the deionized waternozzle body 3237 discharges deionized water to the substrate W.

[0502] On the other hand, the solvent nozzle body 3224 is a tubularmember, of which one end has an opening toward the substrate W and otherend is supplied with an organic solvent from the solvent supplyingsystem. In this way, the solvent nozzle body 3224 discharges the organicsolvent to the substrate W. Incidentally, the distal end of the solventnozzle body 3224 is bent in the direction that the deionized waternozzle body 3237 exist. More specifically, the tip end of the solventnozzle body 3224 is bent so that the reach point with respect to the Wof the organic solvent that has been discharged from the solvent nozzlebody 3224 is equal to the reach point with respect to the substrate W ofthe deionized water that has been discharged from the deionized waternozzle body 3237. With such configuration, both the organic solvent andthe deionized water supplied from the rinse system nozzle 3207 reach tothe same position on the substrate W.

[0503] In the present preferred embodiment, a shown by the arrow 3287 ofFIG. 31, the solvent nozzle body 3224 and the pure nozzle body 3237 aremoved so that both of the reach points with respect to the substrate Wof the deionized water and the organic solvent reciprocally move on thecircular arc whose chord is the radius of the rotation circle 3095 drawnby rotation of the end edge of the substrate W.

[0504] In this configuration, the remover liquid nozzle body 3223, thesolvent nozzle body 3224 and the deionized water nozzle body 3237constitute the remover liquid discharging means, the solvent dischargingmeans and the deionized water discharging means, respectively.

[0505] The direct vibration applying means 3225 is connected to theoscillator, and has a vibrator 3226 which is caused to vibrate by anelectric signal issued from the oscillator, and a vibration bar 3239which vibrates in response to the vibration of the vibrator 3226transmitted thereto.

[0506] The vibration bar 3239 is a bar member crossed in the radialdirection of the rotation circle 3095 and having a length approximatelyequal to the radius of the rotation circle 3095. Furthermore, thevibration bar 3239 is provided above the substrate W at a distancetherefrom as shown in FIG. 32. This distance is such that when a processliquid 3280 is supplied to the substrate W, the vibration bar 3239 comesinto contact with the process liquid 280 thus supplied on the substrateW. FIG. 32 is a cross section view with respect to the F32-F32 of FIG.31.

[0507] In such direct vibration applying means 3225, the vibration bar3239 vibrates while contacting with the process liquid existing on thesubstrate W that has been supplied to the substrate W. Therefore, anultrasonic wave is directly applied to the process liquid existing onthe substrate W.

[0508] In the substrate processing apparatus 3200 as described above, itis possible to perform the substrate processing method which comprises:a remover liquid supplying step in which the substrate W is rotated toreciprocally move the remover liquid nozzle body 3223, the rotatingsubstrate W is supplied with the remover liquid, and the vibration bar3239 contacting with the remover liquid on the substrate W is vibratedto add an ultrasonic wave to the remover liquid existing on the rotatingsubstrate W; a solvent supplying step serving as an intermediate rinsestep in which after the remover liquid supplying step, the rotatingsubstrate W is supplied with the organic solvent while the solventnozzle body 3224 is reciprocally moved, and the vibration bar 3239contacting with the organic solvent supplied on the substrate W isvibrated to add an ultrasonic wave to the organic solvent existing onthe substrate W; a deionized water supplying step in which the rotatingsubstrate W is supplied with the deionized water while the deionizedwater nozzle body 3237 is reciprocally moved, and the vibration bar 3239contacting with the deionized water supplied on the substrate W isvibrated to apply an ultrasonic wave to the deionized water existing onthe substrate W; and a deionized water dispersing step in which thesubstrate W is rotated to disperse the deionized water on the substrateW.

[0509] In this configuration, since an ultrasonic wave is directlyapplied to the process liquid such as remover liquid, organic solventand deionized water existing on the substrate W, the ultrasonic energypossessed by the process liquid in the vicinity of the reaction productsis large compared to the case where the process liquid to which anultrasonic wave has been applied in advance is discharged to thesubstrate W. Therefore, it is possible to desirably remove the reactionproduct.

[0510] While an ultrasonic wave from the vibration bar 3239 is appliedto all of the remover liquid, organic solvent and deionized water on thesubstrate W, it is also possible to add an ultrasonic wave from thevibration bare 3239 to either one or two of the remover liquid, organicsolvent and deionized water on the substrate W.

[0511] The holding and rotating portion of each preferred embodiment asdescribed above rotates the substrate while holding the same in thehorizontal state. Alternatively, the holding and rotating portion may bedesigned to hold and rotate the substrate in the condition that theprincipal surface of the substrate is inclined with respect to thehorizontal surface or the principal surface of the substrate runs alongthe vertical direction.

[0512] While the holding and rotating portion of the each preferredembodiment as described above holds only one substrate, the holding androtating portion may be designed to hold a plurality of substrates.

[0513] An objective of the substrate process in each preferredembodiment as described above is a substrate having a polymer generatedon it surface as a result of dry-etching. However, the substrate processis especially effective in the case where the objective is a substratehaving experienced ashing after the dry-etching.

[0514] Since the liquids such as remover liquid and deionized water aresupplied at least to the center of rotation C of the substrate W and thesubstrate W rotates, the liquids supplied to the substrate are supplieduniformly in the vicinity of the substrate W. In particular, in the casewhere the substrate W is rotated while being held in the horizontalposition, the liquid is uniformly supplied on the entire surface of thesubstrate W, with the result that it is possible to achieve uniformprocess.

[0515] The vacuum chuck 3015 holds the substrate W while contacting onlywith the back surface of the substrate W, and therefore, the liquid isuniformly supplied on the entire surface of the substrate W,particularly in the peripheral part of the surface of the substrate W,so that the quality of process is not deteriorated.

[0516] Furthermore, since the vacuum chuck 3015 holds the substrate Wwhile contacting only with the back surface of the substrate W, nomember contact will contact with the peripheral part of the substrate W.Therefore, when the liquid is dispersed from the substrate W, the liquidcan be discharged from the substrate W smoothly.

[0517] In the above preferred embodiment, it was disclosed that apolymer generated during dry-etching is removed from a substrate thathas experienced the dry-etching, however, the present invention is notlimited to remove a polymer from a substrate on which the polymergenerated during dry-etching.

[0518] For example, as is described before, the present invention alsoincludes the case of removing a polymer generated during plasma ashingfrom the substrate. Therefore, the present invention also includes thecase of removing a polymer generated from a resist in various processesnot limited to dry-etching.

[0519] Furthermore, the present invention is not limited to the case ofremoving the polymer generated in the processes by dry-etching or plasmaashing, but includes the case of removing various reaction productsresulting from a resist from the substrate.

[0520] The present invention is not limited to the case of removingreaction products originating from a resist from the substrate, butincludes the case of removing a resist itself.

[0521] For example, the present invention also includes the case ofremoving a resist film that is no longer required after completion ofthe under layer treatment from a substrate on which a resist is applied,a pattern such as wiring pattern is exposed to the resist, the resist isdeveloped, and an under layer treatment (such as etching to the thinfilm serving as an under layer) is effected on the under layer of theresist.

[0522] In such a case, in addition to removing the resist film which isno longer required, it is possible to remove the reaction products thathave generated as a result of quality change of the resist film ifexists, so that it is possible to improve the throughput and reduce thecost. For example, in the above-mentioned under layer treatment, in thecase where dry-etching is effected on the thin film serving as the underlayer, also the reaction products are generated. Therefore, it ispossible to remove the resist film itself provided for masking the underlayer at the time of dry-etching and the reaction products generated asa result of quality change of the resist film at once.

[0523] Furthermore, the present invention is not limited to the case ofremoving reaction products originating from a resist or a resist itselffrom the substrate, but includes the case of removing micro contaminantsand the like coming, for example, from a human body from a substrate.

[0524] While the deionized water supplying portion is provided in theabove substrate processing apparatus of the preferred embodiment, thedeionized water supplying portion may be replaced by a rinse liquidsupplying portion. In such a case, a rinse liquid source is provided inplace of the deionized water source, and a rinse liquid in the rinseliquid source is supplied to the substrate. In this context, the rinseliquid is a liquid that will turn to water when kept at the atmospherictemperature (about 20° C. to 28° C.) and at the atmospheric pressure(about 1 atmospheric pressure), for example, ozone water in which ozoneis dissolved in deionized water, hydrogen water in which hydrogen isdissolved in deionized water and aerated water in which carbon dioxideis dissolved in deionized water. In particular, by using ozone water asthe rinse liquid in place of the deionized water, it is possible toremove an organic substance, reaction products generated as a result ofquality change of resist and a polymer more completely. Therefore, inthis case, it is possible to solve the problem of improving the qualityof process of removing the an organic substance, reaction productsgenerated as a result of quality change of resist and a polymer.

[0525] In substrate processing method of the above preferred embodiment,the substrate is supplied with the deionized water in the deionizedwater supplying step and the deionized water is dispersed from thesubstrate in the deionized water dispersing step, however, the deionizedwater supplying step may be replaced by the rinse liquid supplying stepand the deionized water dispersing step may be replaced by the rinseliquid dispersing step.

[0526] In such a case, the rinse liquid is supplied to the substrate inthe rinse liquid supplying step and the rinse liquid is dispersed fromthe substrate in the rinse liquid dispersing step.

[0527] Therefore, in the above preferred embodiment, the rinse liquidsupplying step and the rinse liquid dispersing step may be executedsubsequent to the remover liquid dispersing step or the intermediaterinse step.

[0528] In the case where the rinse liquid used in the rinse liquidsupplying step is ozone water, it is possible to remove an organicsubstance, reaction products generated as a result of quality change ofresist and a polymer more completely. Therefore, in the above preferredembodiment, the rinse liquid supplying step and the rinse liquiddispersing step may be executed subsequent to the remover liquiddispersing step or the intermediate rinse step.

[0529] (D. Preferred Embodiments According to Fourth Aspect of thePresent Invention)

[0530] <1 First Preferred Embodiment of the Substrate ProcessingApparatus>

[0531] The following description will discuss a first preferredembodiment of the substrate processing apparatus of the present aspect.

[0532]FIGS. 33 and 34 are drawings that show the construction of asubstrate processing apparatus 4001. FIG. 33 is a cross-sectional viewtaken along line F33-F33 of FIG. 34, and for convenience of explanation,hatching is partially omitted from some portions.

[0533] As illustrated in FIG. 33, the substrate processing apparatus4001 is provided with a cup 4003 which has a virtually U-letter shape inits cross-section, and also has a virtually ring shape with an openingin the center portion thereof as shown in FIG. 34, when viewed fromabove, a holding rotary section 4005 that is formed in a manner so as tostick out through the opening of the cup 4003 in the vertical directionas shown in FIG. 33 and that rotates while holding a substrate W, aremover liquid supplying section 4007 for supplying a remover liquid tothe substrate W held by the holding rotary section 4005 and a deionizedwater supplying section 4009 for also supplying deionized water to thesubstrate W held by the holding rotary section 4005. Moreover, thesubstrate processing apparatus 4001 also has a back surface cleaningnozzle 4011 for supplying deionized water to the back surface of thesubstrate W held by the holding rotary section 4005.

[0534] The cup 4003 has a plurality of discharging outlets 4004 on thebottom thereof. Thus, an excessive portion of the liquid supplied to thesubstrate W drops along the inner wall of the cup 4003 to reach thedischarging outlets 4004, and is discharged out of the apparatus throughthe discharging outlets 4004.

[0535] The holding rotary section 4005, which is secured to an apparatusframe is provided with a spin motor 4013 having a driving shaft placedin the vertical direction and a spin shaft 4014 that is secured to thedriving shaft of the spin motor and a vacuum chuck 4015 serving as asubstrate holding member placed on the top of the spin shaft 4014.

[0536] The vacuum chuck 4015 has a suction surface for applying suctionto the top major surface of the substrate, and the suction surface hasan area smaller than the area of the substrate W when viewed from above.In the present preferred embodiment, the vacuum chuck 4015 is avirtually column-shaped member with the suction surface on the upperportion having a round shape.

[0537] The vacuum chuck 4015 has suction holes in the suction surface onits upper surface, and air is sucked through the suction holes. Thus,the substrate W, placed on the vacuum chuck 4015, is held by air suctionapplied through the suction holes. In this manner, the vacuum chuck 4015holds the substrate W by contacting only the back surface of thesubstrate W.

[0538] In this arrangement, the holding rotary section 4005 holds thesubstrate W placed on the vacuum chuck 4015 through suction applied bythe vacuum chuck 4015, and rotates the substrate W held on the vacuumchuck 4015 around a shaft 4071 serving as the rotation center by drivingthe spin motor 4013.

[0539] The remover liquid supplying section 4007 is provided with afirst rotary motor 4017 which is secured to the apparatus frame and hasa driving shaft placed in the vertical direction, a first rotary shaft4019 secured to the rotary shaft of the first rotary motor 4017 and afirst arm 4021 connected to the top of the first rotary shaft 4019.

[0540] These first rotary motor 4017, first rotary shaft 4019 and firstarm 4021 constitute a first shifting means. The first shifting meansforms a shifting means for shifting a remover liquid discharging meansin the present invention.

[0541] A remover liquid nozzle main body 4023 is installed on the tip ofthe first arm 4021. The remover liquid nozzle main body 4023 constitutesthe remover liquid discharging means.

[0542] The remover liquid nozzle main body 4023 is provided with a firstpassage hole 4029, and a first tube 4027 is connected to the firstpassage hole 4029. The first tube 4027 supplies a remover liquid to thefirst passage hole 4029.

[0543] One end of the first passage hole 4029 is connected to the firsttube 4027 with the other end forming a tube path having an opening tothe top major surface of the substrate W. The extending direction of thefirst passage hole 4029 makes a predetermined angle of inclination withrespect to the top major surface of the substrate W. This angle ofinclination determines an incident angle of the remover liquid to bedischarged from the first passage hole 4029 with respect to the topmajor surface of the substrate W. In other words, the angle ofinclination of the first passage hole 4029 and the incident angle of theremover liquid to be discharged from the first passage hole 4029 withrespect to the substrate W are virtually equal to each other.

[0544] In the present preferred embodiment, the angle of inclination ofthe first passage hole 4029 is set to 45 degrees so that the removerliquid discharged from the first passage hole 4029 reaches the substrateW with an incident angle of 45 degrees.

[0545] Moreover, the remover liquid nozzle main body 4023 is arranged sothat when the first arm 4021 is allowed to pivot centered on the shaft4073 as indicated by arrow 4079, the arrival point of a remover liquid4081 discharged from the first passage hole 4029 (hereinafter, referredto as remover liquid arrival point) with respect to the substrate W isallowed to shift on a line passing through the rotation center C of thesubstrate W and the circumference of a rotation circle 4095 that the endedge of the substrate W forms when the substrate W rotates.

[0546] In the present preferred embodiment, as indicated by arrow 4085of FIG. 34, the remover liquid arrival point is allowed to pass throughthe rotation center C of the substrate W and also to reciprocally shifton a circular arc intersecting the circumference of the rotation circle4095 at two points.

[0547] The line passing through the rotation center C of the substrate Wand the circumference of the rotation circle 4095 that the end edge ofthe substrate W forms when the substrate W rotates may be either astraight line or a curve.

[0548] Moreover, the remover liquid nozzle main body 4023 may be movedso that the remover liquid arrival point is allowed to reciprocallyshift on a circular arc with its chord corresponding to the radius ofthe rotation circle 4095, so that it reciprocally shifts on the radiusof the rotation circle 4095, or so that it reciprocally shifts on thediameter of the rotation circle 4095.

[0549] A first vibrator 4025 is installed inside the first passage hole4029 at a position contacting the remover liquid that passes through thefirst passage hole 4029.

[0550] The first vibrator 4025 is allowed to vibrate by an electricsignal from an oscillator 4067, which will be described later, so as toapply ultrasonic waves to the remover liquid passing through the firstpassage hole 4029.

[0551] The first vibrator 4025 forms a remover liquid vibrator. In theremover liquid supplying section 4017 arranged as described above, thefirst rotary motor 4017 rotates the first rotary shaft 4019 so that thefirst arm 4021 is allowed to reciprocally pivot centered on a shaft4073. Thus, as illustrated in FIG. 34, the remover liquid arrival pointis allowed to reciprocally shift on the substrate W passing through therotation center C of the substrate W in the form of a circular arc asindicated by arrow 4085. Thus, the remover liquid to which ultrasonicwaves are applied is supplied to the substrate W.

[0552] The angle of inclination of the first passage hole 4029 is set toany degrees as long as it is greater than 0 degree, and also smallerthan 90 degrees. However, it is preferably set in the range of not lessthan 30 degrees to not more than 60 degrees, in particular, at 45degrees.

[0553] This arrangement allows the remover liquid to reach the interfaceor border between the reaction products and the surface of the substrateW without having adverse effects from irregularities such as patterns onthe substrate W. In other words, the remover liquid is allowed to reachthe border between the reaction products and the surface of thesubstrate W with less attenuation in the ultrasonic energy.

[0554] Since the ultrasonic wave oscillates along the dischargingdirection of the remover liquid, the remover liquid, which has arrivedat the border between the surface of the substrate W and the reactionproducts, is abundant in energy to try to invade between the reactionproducts and the substrate W. Therefore, the remover liquid is allowedto exert its function below the reaction products strongly so that thereaction products are easily removed from the substrate W, therebymaking it possible to improve the removing efficiency.

[0555] The remover liquid nozzle main body 4023 having the first passagehole 4029 is shifted so that the remover liquid arrival point is allowedto shift on the line passing through the rotation center C of thesubstrate W and the circumference of a rotation circle 4095 that the endedge of the substrate W forms when the substrate W rotates. Therefore,the remover liquid to which the ultrasonic wave is uniformly applied issupplied onto the substrate W. Thus, it is possible to ensure thein-plane uniformity of the substrate in the process while improving theremoving efficiency of the reaction products.

[0556] The deionized water supplying section 4009, which is secured tothe apparatus frame, not shown, is provided with a second rotary motor4031 having a driving shaft placed in the vertical direction, a secondrotary shaft 4033 secured to the driving shaft of the second rotarymotor 4031 and a second arm 4035 that is connected to the top of thesecond rotary shaft 4033.

[0557] These second rotary motor 4031, second rotary shaft 4033 andsecond arm 4035 constitute a second shifting means.

[0558] A deionized water nozzle main body 4037 is installed on the tipof the second arm 4035. The pure nozzle main body 4037 forms a deionizedwater discharging means.

[0559] A second passage hole 4043 that directs the axis line directionof deionized water to be discharged toward the top major surface of thesubstrate W is formed in the pure nozzle main body 4037, and a secondtube 4041 is connected to the second passage hole 4043. The second tube4041 supplies deionized water to the second passage hole 4043.

[0560] One end of the second passage hole 4043 is connected to thesecond tube 4041 with the other end forming a tube path having anopening to the top major surface of the substrate W. Here, the extendingdirection of the second passage hole 4043 makes a predetermined angle ofinclination with respect to the top major surface of the substrate W.This angle of inclination determines an incident angle of the deionizedwater to be discharged from the second passage hole 4043 with respect tothe substrate W. In other words, the angle of inclination of the secondpassage hole 4043 and the incident angle of the deionized water to bedischarged from the second passage hole 4043 with respect to thesubstrate W are virtually equal to each other.

[0561] In the present preferred embodiment, the angle of inclination ofthe second passage hole 4043 is set to 45 degrees so that deionizedwater discharged from the first passage hole 4043 reaches the substrateW with an incident angle of 45 degrees.

[0562] Moreover, the remover liquid nozzle main body 4037 is arranged sothat when the second arm 4035 is allowed to pivot centered on the shaft4075 as indicated by arrow 4077, the arrival point of deionized water4083 discharged from the second passage hole 4043 (hereinafter, referredto as deionized water arrival point) with respect to the substrate W isallowed to shift on a line passing through the rotation center C of thesubstrate W and the circumference of a rotation circle 4095 that the endedge of the substrate W forms when the substrate W rotates.

[0563] In the present preferred embodiment, as indicated by arrow 4087of FIG. 34, the deionized water arrival point is allowed to pass throughthe rotation center C of the substrate W and also to reciprocally shifton a circular arc that intersects the circumference of the rotationcircle 4095 at two points.

[0564] The line passing through the rotation center C of the substrate Wand the circumference of the rotation circle 4095 that the end edge ofthe substrate W forms when the substrate W rotates may be either astraight line or a curve.

[0565] The deionized water nozzle main body 4037 may be moved so thatthe deionized water arrival point is allowed to reciprocally shift on acircular arc with its chord corresponding to the radius of the rotationcircle 4095, so that it reciprocally shifts on the radius of therotation circle 4095, or so that it reciprocally shifts on the diameterof the rotation circle 4095.

[0566] A second vibrator 4039 is installed inside the second passagehole 4043 at a position contacting the deionized water that passesthrough the second passage hole 4043.

[0567] The second vibrator 4039 is allowed to vibrate by an electricsignal from the oscillator 4067, which will be described later, so as toapply ultrasonic waves to the deionized water passing through the secondpassage hole 4043.

[0568] The second vibrator 4039 forms a deionized water vibrator.

[0569] In the deionized water supplying section 4009 arranged asdescribed above, the second rotary motor 4031 rotates the second rotaryshaft 4033 so that the second arm 4035 is allowed to reciprocally pivotcentered on a shaft 4075. Thus, as illustrated in FIG. 34, the deionizedwater arrival point is allowed to reciprocally shift on the substrate Wpassing through the rotation center C of the substrate W in the form ofa circular arc as indicated by arrow 4087. Thus, the deionized water towhich ultrasonic waves are applied is supplied to the substrate W.

[0570] The angle of inclination of the second passage hole 4043 is setto any degrees as long as it is greater than 0 degree, and also smallerthan 90 degrees. However, it is preferably set in the range of not lessthan 30 degrees to not more than 60 degrees, in particular, at 45degrees.

[0571] This arrangement allows the deionized water to reach the borderbetween the reaction products and the surface of the substrate W withouthaving adverse effects from irregularities such as patterns on thesubstrate W. In other words, the deionized water is allowed to reach theborder between the reaction products and the surface of the substrate Wwith less attenuation in the ultrasonic energy.

[0572] Since the ultrasonic wave oscillates along the dischargingdirection of the deionized water, the deionized water, which has arrivedat the border between the surface of the substrate W and the reactionproducts, is abundant in energy to try to invade between the reactionproducts and the substrate W. Therefore, the reaction products arefurther subjected to ultrasonic energy with the result that the reactionproducts are easily removed from the substrate W, thereby making itpossible to improve the removing efficiency.

[0573] The deionized water nozzle body 4037 having the second passagehole 4029 is shifted so that the deionized water arrival point isallowed to shift on the line passing through the rotation center C ofthe substrate W and the circumference of a rotation circle 4095 that theend edge of the substrate W forms when the substrate W rotates;therefore, the deionized water to which the ultrasonic wave is uniformlyapplied is supplied onto the substrate W. Thus, it is possible to ensurethe in-plane uniformity of the substrate in the process while improvingthe removing efficiency of the reaction products.

[0574] A back surface cleaning nozzle 4011 is a tube-shaped member thatpenetrates the cup 4003 and extends virtually in the vertical directiontoward the back major surface of the substrate W, and used for supplyingdeionized water via a back surface cleaning valve 4065, which will bedescribed later. Thus, it is possible to discharge deionized water ontothe back surface of the substrate W.

[0575] Referring to FIG. 35, the following description will discuss aremover liquid supplying system to the remover liquid supplying section4007 as well as a deionized water supplying system 4091 to the deionizedwater supplying section 4009 and the back surface cleaning nozzle 4011.

[0576] The remover liquid supplying system 4089 is provided with aremover liquid pump 4047 for pumping the remover liquid from a removerliquid source 4045 outside the apparatus, a temperature-adjusting device4051 for adjusting the temperature of the remover liquid by heating orcooling the remover liquid pumped out by the remover liquid pump 4047 toa predetermined temperature, a filter 4049 for filtering contaminantsfrom the remover liquid that has been temperature-adjusted by thetemperature-adjusting device 4051, and a remover liquid nozzle valve4053 for opening and closing the flowing path of the filtered removerliquid to the remover liquid supplying section 4007.

[0577] The temperature-adjusting device 4051 forms a remover liquidtemperature-adjusting means, and the remover liquid pump 4047 forms aremover liquid sending means.

[0578] This arrangement allows the remover liquid supplying system 4089to supply the remover liquid that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 4051 andpurified by the filter 4049 to the remover liquid supplying section4007.

[0579] The deionized water supplying system 4091 is provided with adeionized water pump 4057 for pumping deionized water from a deionizedwater source 4055 outside the apparatus, a temperature-adjusting device4061 for adjusting the temperature of the deionized water by heating orcooling the deionized water pumped out by the deionized water pump 4057to a predetermined temperature, a filter 4059 for filtering contaminantsfrom the deionized water that has been temperature-adjusted by thetemperature-adjusting device 4061, and a deionized water nozzle 4063 foropening and closing the flowing path of the filtered deionized waterliquid to the deionized water supplying section 4009 as well as a backsurface cleaning valve 4065 for opening and closing the flowing path ofthe deionized water filtered by the filter 4059 to the back surfacecleaning nozzle.

[0580] The temperature-adjusting device 4061 forms a deionized watertemperature-adjusting means, and the deionized water pump 4057 forms adeionized water sending means.

[0581] This arrangement allows the deionized water supplying system 4091to supply the deionized water that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 4061 andpurified by the filter 4059 to the deionized water supplying section4009.

[0582] Next, referring to FIG. 35, an explanation will be given of aultrasonic wave applying section 4093.

[0583] The ultrasonic wave applying section 4093 is provided with afirst vibrator 4025 placed inside the removing liquid nozzle main body4023 and an oscillator 4067 for vibrating the first vibrator 4025 bytransmitting an electric signal to the first vibrator 4025.

[0584] With this arrangement, the ultrasonic wave applying section 4093applies ultrasonic waves to the remover liquid to be supplied to thesubstrate W from the remover liquid supplying section 4007.

[0585] Moreover, the ultrasonic wave applying section 4093 is alsoprovided with a second vibrator 4039 placed inside the deionized waternozzle main body 4037, and the second vibrator 4039 is vibrated by anelectric signal transmitted from the oscillator 4067.

[0586] With this arrangement, the ultrasonic wave applying section 4093applies ultrasonic waves to the deionized water to be supplied to thesubstrate W from the deionized water supplying section 4009.

[0587] In this manner, the remover liquid with the ultrasonic wavesapplied thereto or the deionized water with the ultrasonic waves appliedthereto is supplied to the substrate W. Therefore, it is possible tocarry out the removing process of the reaction products more quickly,and consequently to improve the throughput. Here, the throughput can beimproved by only applying ultrasonic waves to either the remover liquidor deionized water. However, by applying ultrasonic waves to both of theremover liquid and deionized water, it is possible to remove thereaction products more quickly and to improve the throughput moreeffectively.

[0588] Next, referring to FIG. 4, an explanation will be given of thehardware construction of the substrate processing apparatus 4001.

[0589] To the control means 4069 are connected the spin motor 4013, thefirst rotary motor 4017, the second rotary motor 4031, the oscillator4067, the remover liquid pump 4047, the deionized water pump 4057, theremover liquid nozzle valve 4007, the deionized water nozzle valve 4063,the back surface cleaning valve 4065, the temperature-adjusting device4051 and the temperature-adjusting device 4061. Thus, as will bedescribed in first preferred embodiment and second preferred embodimentof a substrate processing method, the control means 4069 controls thesedevices connected thereto.

[0590] In the substrate processing apparatus 4001 of the presentpreferred embodiment, both of the first vibrator 4025 for applyingultrasonic waves to the remover liquid and the second vibrator 4039 forapplying ultrasonic waves to deionized water are installed. However,either one of them may be installed.

[0591] <2. Second Preferred Embodiment of a Substrate Processing Method>

[0592]FIG. 37 is a drawing that shows a first preferred embodiment of asubstrate processing method in which the above-mentioned substrateprocessing apparatus 4001 is used. As illustrated in FIG. 37, thesubstrate processing method of the present preferred embodiment includesa remover liquid supplying step s4001, a remover liquid spinning-offstep s4002, a deionized water supplying step s4003, and a deionizedwater spinning-off step s4004. Referring to FIG. 38, the followingdescription will discuss the respective steps.

[0593] (1. Remover Liquid Supplying Step s4001)

[0594] First, the control means 4069 has controlled thetemperature-adjusting devices 4051 and 4061 so that the temperatures ofthe remover liquid and deionized water are set to predeterminedtemperatures before the sequence has reached the time t4000.

[0595] Moreover, before the sequence has reached the time t4000, thecontrol means 4069 drives the spin motor 4013 to rotate the substrate Wso that at time t4000, the substrate W is being rotated at apredetermined number of revolutions.

[0596] Then at time t4000, the control means 4069 rotates the firstrotary motor 4017 so as to allow the remover liquid supplying section4007 to pivot.

[0597] Furthermore, at the time t4000, the control means 4069 drives theremover liquid pump 4047 so as to send the remover liquid to the removerliquid supplying section 4007, and also allows the remover liquid nozzlevalve 4053 to open so as to supply the remover liquid from the removerliquid supplying section 4007 to the substrate W. With these steps, theremover liquid, supplied from the remover liquid supplying section 4007,is supplied onto the substrate W in such a manner that the arrival pointthereof onto the substrate W is shifted on a circular arc passingthrough the rotation center C of the substrate W in the horizontalsurface including the surface of the substrate W as indicated by arrow4085 in FIG. 34. In this manner, the remover liquid supplying step s4001is executed.

[0598] Here, at time t4000, the control means 4069 allows the oscillator4067 to transmit an electric signal to the first vibrator 4025 withinthe remover liquid supplying section 4007 so as to oscillate the firstvibrator 4025. Thus, ultrasonic waves are applied to the remover liquidsupplied from the remover liquid supplying section 4007. Consequently,the reaction products adhering to the substrate W are subjected toultrasonic vibration, and thus easily separated from the substrate W.

[0599] At the time t4001 after a lapse of a predetermined time, thecontrol means 4069 stops the driving operation of the first rotary motor4017 in a state where the remover liquid supplying section 4007 hasretreated from a position above the cup 4003. Moreover, the controlmeans 4069 closes the remover liquid nozzle valve 4053, and also stopsthe driving operation of the remover liquid pump 4047 so as to stop thesupply of the remover liquid from the remover liquid supplying section4007. Moreover, at time t4001, the control means 4069 stops thetransmission of the electric signal from the oscillator 4067 to thefirst vibrator 4025.

[0600] In this manner, the remover liquid arrival point is shifted onthe circular arc passing through the rotation center C of the substrateW so that the remover liquid that is less susceptible to temperaturechanges and that is fresh without being exhausted can be supplied to theentire portion of the substrate W; thus, it is possible to easily removethe reaction products and also to ensure the in-plane uniformity in theentire surface of the substrate W.

[0601] (2. Remover Liquid Spinning-Off Step s4002)

[0602] Next, at the time t4001, the control means 4069 stops the supplyof the remover liquid to the substrate W, while it successively rotatesthe spin motor 4013 so as to maintain the rotating state of thesubstrate W. Thus, a remover liquid spinning-off step s4002 is executed.

[0603] In this remover liquid spinning-off step s4002, the substrate Wis rotated at not less than 500 rpm, more preferably, in the range from1000 rpm to 4000 rpm.

[0604] Moreover, the time during which the rotation is maintained is setto not less than 1 second, preferably, in the range of 2 to 5 seconds.

[0605] In this manner, the rotating state of the substrate is maintainedwith the supply of the remover liquid being stopped with respect to thesubstrate W, the remover liquid on the substrate W is spun off from thesubstrate W by a centrifugal force.

[0606] Furthermore, since the substrate is rotated while beingmaintained in the horizontal state, the remover liquid is spun off fromthe substrate W uniformly. Thus, it is possible to maintain the in-planeuniformity of the substrate W.

[0607] Here, since the vacuum chuck 4015 is kept in contact with onlythe back surface of the substrate W, there are no parts contacting theedge of the substrate W. Consequently, since there are no parts thatintervene with the progress the remover liquid that is spun off in thehorizontal direction toward the outside of the substrate W from the topmajor surface of the substrate W, the time required for the removerliquid to be spun off from the substrate is shortened. Thus, it ispossible to improve the throughput.

[0608] Moreover, since the holding rotary section 4005 only needs tohold a single sheet of the substrate W, it is possible to easilyincrease the number of revolutions of the substrate W. For this reason,the time required for the remover liquid to be spun off from thesubstrate is shortened. Thus, it is possible to improve the throughput.

[0609] (3. Deionized Water Supplying Step s4003)

[0610] Next, at the time t4002, the control means 4069 rotates thesecond rotary motor 4032 so as to allow the deionized water supplyingsection 4009 to pivot.

[0611] At the time t4002 also, the control means 4069 drives thedeionized water pump 4057 so as to send deionized water to the deionizedwater supplying section 4009, and also allows the deionized water nozzlevalve 4063 to open so as to supply the deionized water from thedeionized water supplying section 4009 to the substrate W. With thesesteps, the deionized water, supplied from the deionized water supplyingsection 4009, is supplied onto the substrate W in such a manner that thearrival point thereof onto the substrate W is shifted on a circular arcpassing through the rotation center C of the substrate W in thehorizontal surface including the surface of the substrate W as indicatedby arrow 4087 in FIG. 34. In this manner, the deionized water supplyingstep s4003 is executed.

[0612] At the time t4002, the control means 4069 allows the oscillator4067 to transmit an electric signal to the second vibrator 4039 withinthe deionized water supplying section 4009 so as to oscillate the secondvibrator 4039. Thus, ultrasonic waves are applied to the deionized watersupplied from the deionized water supplying section 4009. Consequently,the reaction products adhering to the substrate W are subjected toultrasonic vibration, and thus easily separated from the substrate W.

[0613] Moreover, at the time t4002, the control means 4069 allows theback surface cleaning valve 4065 to open so as to supply deionized waterto the back surface of the substrate W from the back surface cleaningnozzle 4011, thereby also cleaning the back surface of the substrate W.

[0614] At the time t4003 after a lapse of a predetermined time period,the control means 4069 stops the driving operation of the second rotarymotor 4031 in a state where the deionized water supplying section 4009has retreated from a position above the cup 4003. Moreover, the controlmeans 4069 closes the deionized water nozzle valve 4063, and also stopsthe driving operation of the deionized water pump 4057 so as to stop thesupply of the deionized water from the deionized water supplying section4009. Moreover, at the time t4003, the control means 4069 stops thetransmission of the electric signal from the oscillator 4067 to thesecond vibrator 4039.

[0615] In this manner, the deionized water arrival point is shifted onthe circular arc passing through the rotation center C of the substrateW so that the deionized water that is less susceptible to temperaturechanges and that is fresh without being exhausted can be supplied to theentire portion of the substrate W. Thus, it is possible to easily removethe reaction products and also to ensure the in-plane uniformity in theentire surface of the substrate W.

[0616] (4. Remover Liquid Spinning-Off Step s4004)

[0617] At the time t4003, the control means 4069 stops the supply of thedeionized water to the substrate W, while it successively rotates thespin motor 4013 so as to maintain the rotating state of the substrate W.Thus, a deionized water spinning-off step s4004 is executed.

[0618] In this manner, the remover liquid and deionized water aresupplied to the substrate W so that the reaction products are removed.

[0619] In accordance with the present preferred embodiment, at theremover liquid spinning-off step s4002, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W becomes very little, or no longer exists. Therefore, in thecase when, in this state, the deionized water is supplied to thesubstrate W at the deionized water supplying step s4003, the amount ofthe remover liquid that comes to contact the deionized water becomesvery little or none. Therefore, even in the event of a pH shock, hardlyany adverse effect is given to the substrate W, or no pH shock occurs.Therefore, no intermediate rinse process is required, and the throughputis consequently improved. Moreover, by omitting the intermediate rinseprocess, the costs can be reduced, and since an organic solvent, usedfor the intermediate rinse process, is no longer required, it ispossible to improve the safety of the apparatus.

[0620] Since the remover liquid and deionized water to which ultrasonicwaves have been applied are supplied, it is possible to remove thereaction products more quickly.

[0621] In the substrate processing method of the present preferredembodiment, the rotation of the substrate W has not been stopped fromthe start of the remover liquid supplying step s4001 to the completionof the deionized water spinning-off step s4004. However, the rotation ofthe substrate W may be temporarily stopped at any one of the intervalsbetween the remover liquid supplying step s4001 and the remover liquidspinning-off step s4002, between the remover liquid spinning-off steps4002 and the deionized water supplying step s4003 and between thedeionized water supplying step s4003 and the deionized waterspinning-off step s4004.

[0622] The essential thing is to provide at least a step for reducingthe remover liquid on the substrate W by rotating the substrate W evenin a short time, prior to the start of the deionized water supplyingstep s4003.

[0623] Moreover, with respect to the number of revolutions of thesubstrate W, it may be the same or respectively different in the removerliquid supplying step s4001, the remover liquid spinning-off step s4002,the deionized water supplying step s4003 and the deionized waterspinning-off step s4004.

[0624] In the substrate processing method of the present preferredembodiment, ultrasonic waves are applied to both of the remover liquidand deionized water. However, ultrasonic waves may be applied to onlyeither of the remover liquid and deionized water.

[0625] <3. Second Preferred Embodiment of the Substrate ProcessingMethod>

[0626] Referring to FIG. 39, an explanation will be given of thesubstrate processing method in accordance with a second preferredembodiment.

[0627] The substrate processing method of the second preferredembodiment repeats the substrate processing method of the firstpreferred embodiment twice.

[0628] In other words, the substrate processing method of the presentinvention includes a first remover liquid supplying step s4011, a firstremover liquid spinning-off step s4012, a first deionized watersupplying step s4013, a first deionized water spinning-off processs4014, a second remover liquid supplying step s4021, a second removerliquid spinning-off step s4022, a second deionized water supplying steps4023 and a second deionized water spinning-off step s4024.

[0629] The first remover liquid supplying step s4011 and the secondremover liquid supplying step s4021 are the same as the remover liquidsupplying step s4001 of the first preferred embodiment.

[0630] Moreover, the first remover liquid spinning-off step s4012 andthe second remover liquid spinning-off step s4022 are the same as theremover liquid spinning-off step s4002 of the first preferredembodiment.

[0631] The first deionized water supplying step s4013 and the seconddeionized water supplying step s4023 are the same as the deionized watersupplying step s4003 of the first preferred embodiment.

[0632] The first deionized water spinning-off step s4014 and the seconddeionized water spinning-off step s4024 are the same as the deionizedwater spinning-off step s4004 of the first preferred embodiment.

[0633] In the substrate processing method of the second preferredembodiment, the first deionized water spinning-off step s4014 is placedbetween the first deionized water supplying step s4013 and the secondremover liquid supplying step s4021. For this reason, the deionizedwater, which has been supplied on the substrate W at the first deionizedwater supplying step s4013, is spun off by the first deionized waterspinning-off process s4014 so that the remaining deionized water on thesubstrate W becomes very little or none. Therefore, in the case when, inthis state, the remover liquid is supplied to the substrate W, theamount of the deionized water that comes to contact the remover liquidbecomes very little or none; consequently, even in the event of a pHshock, hardly any adverse effect is given to the substrate W, or no pHshock occurs.

[0634] In the present preferred embodiment, the substrate processingmethod of the first preferred embodiment is repeated twice. However,this method may be repeated not less than twice.

[0635] <4. Second Preferred Embodiment of the Substrate ProcessingApparatus>

[0636] Referring to FIGS. 40 and 41, an explanation will be given of asecond preferred embodiment of the substrate processing apparatus of thepresent invention. Here, FIG. 41 is a cross-sectional view taken alongline F41-F41 of FIG. 40; and, for convenience of explanation, hatchingis omitted from some portions.

[0637] A substrate processing apparatus 4100 of the second preferredembodiment is provided with a solvent supplying section 4002 serving asan intermediate rinse supplying section, in addition to the substrateprocessing apparatus 4001 of the first preferred embodiment.

[0638] The substrate processing apparatus 4100 of the second preferredembodiment has many parts that are in common with the substrateprocessing apparatus 4001 of the first preferred embodiment, andtherefore, the corresponding parts are indicated by the same referencenumerals, and description thereof is omitted.

[0639] As illustrated in FIG. 40, the substrate processing apparatus4100 has the solvent supplying section 4002.

[0640] The solvent supplying section 4002, which is secured to theapparatus frame, not shown, is provided with a third rotary motor 4018having a driving shaft placed in the vertical direction, a third rotaryshaft 4020 secured to the rotary shaft of the third rotary motor 4018and a third arm 4022 connected to the top of the third rotary shaft4020.

[0641] These third rotary motor 4018, third rotary shaft 4020 and thirdarm 4022 constitute a third shifting means.

[0642] A solvent nozzle main body 4024 is installed on the tip of thethird arm 4022.

[0643] The solvent nozzle main body 2024 constitutes an intermediaterinse liquid discharging means.

[0644] The solvent nozzle main body 4024 is provided with a thirdpassage hole 4030 that directs the axis line direction of an organicsolvent to be discharged toward the top surface of the substrate W, anda third tube 4028 is connected to the third passage hole 4030. The thirdtube 4028 supplies the organic solvent to the third passage hole 4030.

[0645] One end of the third passage hole 4030 is connected to the thirdtube 4028 with the other end forming a tube path having an opening tothe top major surface of the substrate W. Here, the extending directionof the third passage hole 4030 makes a predetermined angle ofinclination with respect to the top major surface of the substrate W.This angle of inclination determines an incident angle of the organicsolvent to be discharged from the third passage hole 4030 with respectto the top major surface of the substrate W. In other words, the angleof inclination of the third passage hole 4030 and the incident angle ofthe organic solvent to be discharged from the third passage hole 4030with respect to the substrate W are virtually equal to each other.

[0646] In the present preferred embodiment, the angle of inclination ofthe third passage hole 4030 is set to 45 degrees so that the organicsolvent discharged from the third passage hole 4030 reaches thesubstrate W with an incident angle of 45 degrees.

[0647] The solvent nozzle main body 4024 is arranged so that when thethird arm 4022 is allowed to pivot centered on the shaft 4074 asindicated by arrow 4078, the arrival point of an organic solvent 4082discharged from the third passage hole 4030 (hereinafter, referred to assolvent arrival point) with respect to the substrate W is allowed toshift on a line passing through the rotation center C of the substrate Wand the circumference of a rotation circle 4095 that the end edge of thesubstrate W forms when the substrate W rotates.

[0648] In the present preferred embodiment, as indicated by arrow 4086of FIG. 40, the solvent arrival point is allowed to shift on a circulararc passing through the rotation center C of the substrate W.

[0649] The line passing through the rotation center C of the substrate Wand the circumference of the rotation circle 4095 that the end edge ofthe substrate W forms when the substrate W rotates may be either astraight line or a curve.

[0650] The solvent nozzle main body 4024 may be moved so that thesolvent arrival point is allowed to shift on a circular arc with itschord corresponding to the radius of the rotation circle 4095, so thatit shifts on the radius of the rotation circle 4095, or so that itshifts on the diameter of the rotation circle 4095.

[0651] A third vibrator 4026 is installed inside the third passage hole4030 at a position contacting the organic solvent that passes throughthe third passage hole 4030.

[0652] The third vibrator 4026 is allowed to vibrate by an electricsignal from an oscillator 4067 so as to apply ultrasonic waves to theorganic solvent passing through the third passage hole 4030.

[0653] The third vibrator 4026 forms a solvent vibrator.

[0654] In the solvent supplying section 4002 arranged as describedabove, the third rotary motor 4018 rotates the third rotary shaft 4020so that the third arm 4022 is allowed to reciprocally pivot centered ona shaft 4074 as indicated by arrow 4078. Thus, as illustrated in FIG.40, the solvent arrival point of the solvent discharged from the solventsupplying section 4002 is allowed to reciprocally shift on the substrateW passing through the rotation center C of the substrate W in the formof a circular arc as indicated by arrow 4086. Thus, the organic solventto which ultrasonic waves are applied is supplied to the substrate W.

[0655] The angle of inclination of the third passage hole 4030 is set toany degrees as long as it is greater than 0 degree, and also smallerthan 90 degrees. However, it is preferably set in the range of not lessthan 30 degrees to not more than 60 degrees, in particular, at 45degrees.

[0656] This arrangement allows the organic solvent to reach the borderbetween the reaction products and the surface of the substrate W withouthaving much adverse effects from irregularities such as patterns on thesubstrate W. In other words, the organic solvent is allowed to reach theborder between the reaction products and the surface of the substrate Wwith less attenuation in the ultrasonic energy.

[0657] Since the ultrasonic wave oscillates along the dischargingdirection of the organic solvent, the organic solvent, which has arrivedat the border between the surface of the substrate W and the reactionproducts, is abundant in energy to try to invade between the reactionproducts and the substrate W. Therefore, the organic solvent is allowedto exert its function below the reaction products strongly so that theremover liquid located below the reaction products is desirably removedfrom the substrate W. Moreover, since the reaction products on thesubstrate W is further subjected to ultrasonic energy so that thereaction products are easily removed from the substrate W, therebymaking it possible to improve the removing efficiency.

[0658] The organic solvent nozzle main body 4024 having the thirdpassage hole 4030 is shifted so that the organic solvent arrival pointis allowed to shift on the line passing through the rotation center C ofthe substrate W and the circumference of a rotation circle 4095 that theend edge of the substrate W forms when the substrate W rotates;therefore, the organic solvent to which the ultrasonic wave is uniformlyapplied is supplied onto the substrate W. Thus, it is possible to ensurethe in-plane uniformity of the substrate in the process while improvingthe removing efficiency of the reaction products.

[0659] Since the remover liquid remaining in the vicinity of the borderbetween the reaction products and the substrate W is desirably cleaned,it is possible to desirably remove the remover liquid from the substrateW. For this reason, even when deionized water is supplied to thesubstrate W in the deionized water supplying process, which will bedescribed later, the apparatus is less susceptible to the occurrence ofa pH shock.

[0660] A back surface solvent nozzle 4012 is a tube-shaped member thatpenetrates the cup 4003 and extends virtually in the vertical directiontoward the back surface of the substrate W, and used for supplying theorganic solvent via a back surface solvent valve 4066, which will bedescribed later. Thus, it is possible to discharge the organic solventonto the back surface of the substrate W.

[0661]FIG. 42 shows an organic solvent supplying system for supplyingthe organic solvent to the organic solvent supplying section 4002.

[0662] The organic solvent supplying system is provided with a solventpump 4048 for pumping the organic solvent from an organic solvent source4046 outside the apparatus, a temperature-adjusting device 4052 foradjusting the temperature of the organic solvent by heating or coolingthe organic solvent pumped out by the solvent pump 4048 to apredetermined temperature, a filter 4050 for filtering contaminants fromthe organic solvent that has been temperature-adjusted by thetemperature-adjusting device 4052, a solvent nozzle valve 4054 foropening and closing the flowing path of the filtered organic solvent tothe solvent supplying section 4002, and a back surface solvent valve4066 for opening and closing the flowing path of the organic solventfiltered by the filter 4050 to the back surface solvent nozzle 4012.

[0663] The temperature-adjusting device 4052 forms a solventtemperature-adjusting means, and the solvent pump 4048 forms a solventsending means.

[0664] This arrangement allows the solvent supplying system to supplythe organic solvent that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 4052 andpurified by the filter 4050 to the solvent nozzle main body 4024.

[0665] Moreover, the ultrasonic wave applying section 4093 is providedwith a third vibrator 4026 placed inside the solvent supplying section4002, and the third vibrator 4026 is allowed to vibrate by an electricsignal transmitted from the oscillator 4067.

[0666] With this arrangement, the ultrasonic wave applying section 4093applies ultrasonic waves to the organic solvent to be supplied from thesolvent supplying section 4002.

[0667] In this manner, the organic solvent with the ultrasonic wavesapplied thereto is supplied to the substrate W. Therefore, it ispossible to carry out the removing process of the reaction products morequickly, and consequently to improve the throughput. The throughput canbe improved by only applying ultrasonic waves to any one of the removerliquid, the organic solvent and deionized water. However, by applyingultrasonic waves to any two or all of the remover liquid, the organicsolvent and deionized water, it becomes possible to remove the reactionproducts more quickly and to improve the throughput more effectively.

[0668] Next, referring to FIG. 43, an explanation will be given of thehardware construction of the substrate processing apparatus 4100.

[0669] In the same manner as the control means 4069 in the firstpreferred embodiment, to the control means 4070 are connected the spinmotor 4013, the first rotary motor 4017, the second rotary motor 4031,the oscillator 4067, the remover liquid pump 4047, the deionized waterpump 4057, the remover liquid nozzle valve 4007, the deionized waternozzle valve 4063, the back surface cleaning valve 4065, thetemperature-adjusting device 4051 and the temperature-adjusting device4061.

[0670] Moreover, to the control means 4070 are further connected thethird rotary motor 4018, the solvent pump 4048, the solvent nozzle 4054,the back surface solvent valve 4066 and the temperature-adjusting device4052.

[0671] Thus, as will be described in a third preferred embodiment of asubstrate processing method, the control means 4070 controls thesedevices connected thereto.

[0672] In the substrate processing apparatus 4100 of the presentpreferred embodiment, three vibrators, that is, the first vibrator 4025for applying ultrasonic waves to the remover liquid, the second vibrator4039 for applying ultrasonic waves to deionized water and the thirdvibrator 4026 for applying ultrasonic waves to the organic solvent areinstalled. However, any one of these, or any two of these may beinstalled.

[0673] <5. Third Preferred Embodiment of the Substrate ProcessingMethod>

[0674] Referring to FIG. 44, an explanation will be given of thesubstrate processing method in accordance with a third preferredembodiment in which the above-mentioned substrate processing apparatus4100 is used.

[0675] The substrate processing method of the present preferredembodiment is provided with: a remover liquid supplying step s4031, aremover liquid spinning-off step s4032, a solvent supplying step s4033serving as an intermediate rinse step, a deionized water supplying steps4034 and a deionized water spinning-off process s4035.

[0676] The substrate processing method of the present preferredembodiment is virtually designed by interpolating the solvent supplyingstep between the remover liquid spinning-off step s4002 and thedeionized water supplying step s4003 in the substrate processing methodof the first preferred embodiment including the remover liquid supplyingstep s4001, the remover liquid spinning-off step s4002, the deionizedwater supplying step s4003 and the deionized water spinning-off processs4004.

[0677] Therefore, the above-mentioned remover liquid supplying steps4031, the remover liquid spinning-off step s4032, the deionized watersupplying step s4034 and the deionized water spinning-off step s4035 arerespectively the same as the remover liquid supplying step s4001, theremover liquid spinning-off step s4002, the deionized water supplyingstep s4003 and the deionized water spinning-off step s4004 in thesubstrate processing method of the first preferred embodiment;therefore, the description thereof is omitted.

[0678] Next, an explanation will be given of the solvent supplying steps4033 of the present preferred embodiment. As illustrated in FIG. 45,the solvent supplying step s4033 is carried out after the remover liquidsupplying step s4031 and the remover liquid spinning-off step s4032 havebeen finished. In the remover liquid spinning-off process s4032, thesubstrate is kept rotating with the supply of the remover liquid to thesubstrate W being stopped so that the remover liquid on the substrate Wis spun off from the substrate W by a centrifugal force; thus, theremover liquid remaining on the substrate W is reduced to a minimum.

[0679] Next, at time t4002, the control means 4070 rotates the thirdrotary motor 4018, thereby allowing the solvent supplying section 4002to pivot.

[0680] At time t4002 also, the control means 4070 drives the solventpump 4048 so as to send the organic solvent to the solvent supplyingsection 4002, also drives the temperature-adjusting device 4052 to setthe organic solvent to a predetermined temperature, and then opens thesolvent nozzle valve 4054 so as to supply the organic solvent from thesolvent supplying section 4002. With these steps, the organic solvent,supplied from the solvent supplying section 4002, is supplied onto thesubstrate W in such a manner that the arrival point thereof onto thesubstrate W is shifted on a circular arc passing through the rotationcenter C of the substrate W in the horizontal surface including thesurface of the substrate W as indicated by arrow 4086 in FIG. 40. Inthis manner, the solvent supplying step s4033 is executed.

[0681] Here, at time t4002, the control means 4070 allows the oscillator4067 to transmit an electric signal to the third vibrator 4026 withinthe solvent supplying section 4002 so as to vibrate the third vibrator4026. Thus, ultrasonic waves are applied to the organic solvent suppliedfrom the solvent supplying section 4002.

[0682] Consequently, the reaction products adhering to the substrate Ware subjected to ultrasonic vibration, and thus easily separated fromthe substrate W.

[0683] Moreover, at time t4002, the control means 4070 allows the backsurface solvent valve 4066 to open so as to supply the organic solventto the back surface of the substrate W from the back surface solventnozzle 4012, thereby also cleaning the remover liquid away from the backsurface of the substrate W.

[0684] As described above, in the solvent supplying step s4033, theremover liquid is completely washed away from the substrate W bysupplying the organic solvent to the substrate W. For this reason, evenwhen deionized water is supplied to the substrate W in the succeedingdeionized water supplying step s4034, the remover liquid contactingdeionized water no longer exists, thereby making it possible to preventthe occurrence of a pH shock. Consequently, it becomes possible toprevent damages to thin films on the substrate W.

[0685] Moreover, the solvent arrival point is shifted on the circulararc passing through the rotation center C of the substrate W so that theorganic solvent that is less susceptible to temperature changes and thatis fresh without being exhausted can be supplied to the entire portionof the substrate W; thus, it is possible to positively remove theremover liquid from the entire surface of the substrate W and also toensure the in-plane uniformity in the entire surface of the substrate W.

[0686] In the present preferred embodiment, since the remover liquid hasbeen spun off from the substrate W in the remover liquid spinning-offstep s4032, the remover liquid remaining on the substrate W at thispoint of time is very little. For this reason, it is possible to shortenthe time required for the organic solvent to remove the remover liquidin the solvent supplying process s4033. Thus, it becomes possible toimprove the throughput. In the same manner, since the remover liquidremaining on the substrate W is very little, it is possible to reducethe amount of the organic solvent to be required for the solventsupplying step s4033, and consequently to reduce the costs.

[0687] Here, in the present preferred embodiment, the deionized watersupplying step s4034 is executed immediately after the solvent supplyingstep s4033. However, a solvent spinning-off process for spinning thesolvent on the substrate W off may be placed between the solventsupplying step s4033 and the deionized water supplying step s4034.

[0688] Moreover, in the present preferred embodiment, the rotation ofthe substrate W has not been stopped from the start of the removerliquid supplying step s4031 to the completion of the deionized waterspinning-off step s4035. However, the rotation of the substrate W may betemporarily stopped at any one of the intervals between the removerliquid supplying process s4031 and the remover liquid spinning-off steps4032, between the remover liquid spinning-off step s4032 and thesolvent supplying step s4033, between the solvent supplying step s4033and the deionized water supplying step s4034, and between the deionizedwater supplying step s4034 and the deionized water spinning-off steps4035.

[0689] The essential thing is to provide at least a step for reducingthe remover liquid on the substrate W by rotating the substrate W evenin a short time, prior to the start of the solvent supplying step s4033.Consequently, it is possible to shorten the time required for thesolvent supplying step s4035, to improve the throughput, and also toreduce the costs.

[0690] Moreover, in the present preferred embodiment, the removerliquid, the organic solvent and deionized water to which ultrasonicwaves are applied are supplied so that it is possible to remove thereaction products more quickly.

[0691] Furthermore, in the present preferred embodiment, a sequence ofsteps including the remover liquid supplying step s4031, the removerliquid spinning-off step s4032, the solvent supplying step s4033, thedeionized water supplying step s4034 and the deionized waterspinning-off step s4035 are carried out once. However, this sequence ofsteps may be repeated several times.

[0692] <6. Third Preferred Embodiment of the Substrate ProcessingApparatus>

[0693] Referring to FIGS. 46 and 47, an explanation will be given of asubstrate processing apparatus in accordance with a third preferredembodiment of the present invention. Here, FIG. 47 is a top view of FIG.46.

[0694] A substrate processing apparatus 4200 in accordance with thethird preferred embodiment is greatly distinct from the substrateprocessing apparatus 4001 of the first preferred embodiment and thesubstrate processing apparatus 4100 of the second preferred embodimentin that no vibrators for applying ultrasonic waves to the processliquids are placed inside the nozzles for discharging the processliquids such as the remover liquid, the intermediate rinse liquid anddeionized water, and in that, instead of these, a directvibration-applying means, which contacts the process liquids dischargedonto a substrate and located on the substrate to directly applyultrasonic waves thereto, is provided.

[0695] Moreover, the substrate processing apparatus 4200 is distinctfrom the substrate processing apparatus 4100 of the second preferredembodiment in that the solvent nozzle main body and the deionized waternozzle main body are installed on one arm. However, the otherconstructions including the holding rotary section, the remover liquidsupplying system, the solvent supplying system and the deionized watersupplying system are virtually the same as those of the second preferredembodiment; therefore, explanations will be given of only the differentparts.

[0696] As illustrated in FIG. 46, the substrate processing apparatus4200 is provided with a remover liquid supplying section 4207 forsupplying a remover liquid to a substrate W, a solvent and deionizedwater supplying section 4209 for supplying an organic solvent anddeionized water to the substrate W and a direct vibration-applying means4225. Here, not shown in the Figure, the substrate W is held on theholding rotary section in the same manner as the substrate processingapparatus 4100.

[0697] The remover liquid supplying section 4207, which is secured to anapparatus frame, not shown, is provided with a first rotary motor 4217having a driving shaft directed in the vertical direction, a firstrotary shaft 4219 secured to the driving shaft of the first rotary motor4217, and a first arm 4221 connected to the top of the first rotaryshaft 4219.

[0698] A first fixing block 4229 is installed on the tip of the firstarm 4221, and a remover liquid nozzle main body 4223 is attached to thefirst fixing block 4229.

[0699] The remover liquid nozzle main body 4223 is a tube-shaped memberplaced in the vertical direction, and one end thereof has an openingdirected to the substrate W and the remover liquid is supplied to theother end thereof from the remover liquid supplying system. Thus, theremover liquid nozzle main body 4223 is allowed to discharge the removerliquid to the substrate W.

[0700] Here, as indicated by arrow 4285 in FIG. 47, in the presentpreferred embodiment, the remover liquid nozzle main body 4223 isshifted so that the arrival point of the remover liquid with respect tothe substrate W is allowed to shift on a circular arc with its chordcorresponding to the radius of a rotation circle 4095 that the end edgeof the substrate W forms when it rotates.

[0701] The solvent and deionized water supplying section 4209, which issecured to an apparatus frame, not shown, is provided with a secondrotary motor 4231 having a driving shaft directed in the verticaldirection, a second rotary shaft 4233 secured to the driving shaft ofthe second rotary motor 4231, and a second arm 4235 connected to the topof the second rotary shaft 4233.

[0702] A second fixing block 4243 is installed on the tip of the secondarm 4235, and a deionized water nozzle main body 4237 and a solventnozzle main body 4224 are attached to the second fixing block 4243.

[0703] The deionized water nozzle main body 4237 is a tube-shaped memberplaced in the vertical direction, and one end thereof has an openingdirected to the substrate W and deionized water is supplied to the otherend thereof from the deionized water supplying system. Thus, thedeionized water nozzle main body 4237 is allowed to discharge thedeionized water to the substrate W.

[0704] The solvent nozzle main body 4224 is a tube-shaped member placedin the vertical direction, and one end thereof has an opening directedto the substrate W and the organic solvent is supplied to the other endthereof from the solvent supplying system. Thus, the solvent nozzle mainbody 4224 is allowed to discharge the organic solvent to the substrateW. Here, the tip of the solvent nozzle main body 4224 is bent toward thelocation of the pure nozzle main body 4237. More specifically, the tipof the solvent nozzle main body 4224 is bent in such a manner that thearrival point to the substrate W of the organic solvent discharged fromthe solvent nozzle main body 4224 and the arrival point to the substrateW of the deionized water discharged from the deionized water nozzle mainbody 4237 are made coincident with each other. With this arrangement,both of the organic solvent and deionized water supplied from arinse-related nozzle 4207 are allowed to arrive at the same position onthe substrate W.

[0705] As indicated by arrow 4287 in FIG. 47, in the present preferredembodiment, the solvent nozzle main body 4224 and the deionized waternozzle main body 4237 are shifted so that both of the arrival points ofthe deionized water and the organic solvent with respect to thesubstrate W are allowed to shift on a circular arc with its chordcorresponding to the radius of a rotation circle 4095 that the end edgeof the substrate W forms when it rotates.

[0706] In this case, the remover liquid nozzle main body 4223, thesolvent nozzle main body 4224 and the deionized water nozzle main body4237 respectively constitute a remover liquid discharging means, asolvent discharging means and a deionized water discharging means.

[0707] The direct vibration applying means 4225 is connected to anoscillator, not shown, and is provided with a vibrator 4226 forgenerating vibration by an electric signal transmitted from theoscillator and a vibration rod 4239 that is allowed to vibrate byvibration transmitted from the vibrator 4226.

[0708] The vibration rod 4239, which is a rod-shaped member having alength virtually covers the radius of the rotation circle 4095, ispassed over the rotation circle 4095 in the radial direction. Moreover,as illustrated in FIG. 48, the vibration rod 4239 is placed above thesubstrate W with a gap. This gap is determined in such a manner thatwhen a process liquid 4280 is supplied to the substrate W, the vibrationrod 4239 is allowed to contact the process liquid 4280 thus suppliedonto the substrate W. Here, FIG. 48 is a cross-sectional view takenalong line F48-F48 of FIG. 47.

[0709] In this manner, the direct vibration applying means 4225 isallowed to vibrate with the vibration rod 4239 contacting the processliquid supplied to the substrate W and located on the substrate W. Thus,the process liquid on the substrate W is directly subjected toultrasonic vibration.

[0710] In the substrate processing apparatus 4200 as described above, itis possible to carry out a substrate processing method including theremover liquid supplying step in which: the substrate W is rotated sothat the remover liquid nozzle main body 4223 is reciprocally shifted,the remover liquid is supplied to the rotating substrate W, and thevibration rod 4239 contacting the remover liquid on the substrate W isvibrated so that ultrasonic waves are applied to the remover liquidlocated on the rotating substrate W; the solvent supplying step servingas an intermediate rinse step in which: after the remover liquidsupplying step, the organic solvent is supplied to the rotatingsubstrate W while reciprocally shifting the solvent nozzle main body4224, and the vibration rod 4239 contacting the organic solvent suppliedonto the substrate W is vibrated so that ultrasonic waves are applied tothe organic solvent located on the substrate W; the deionized watersupplying step in which: the deionized water is supplied to the rotatingsubstrate W while reciprocally shifting the deionized water nozzle mainbody 4237, and the vibration rod 4239 contacting the deionized watersupplied onto the substrate W is vibrated so that ultrasonic waves areapplied to the deionized water located on the rotating substrate W; andthe deionized water spinning-off step for spinning the deionized wateroff from the substrate W by rotating the substrate W.

[0711] In this case, since ultrasonic waves are directly applied to theprocess liquids such as the remover liquid, the organic solvent and thedeionized water located on the substrate W so that, in comparison with acase in which process liquids to which ultrasonic waves have beenpreliminarily applied are discharged onto the substrate, the processliquids in the vicinity of the reaction products have greater ultrasonicenergy. Therefore, it is possible to desirably remove the reactionproducts.

[0712] In this case, ultrasonic waves are applied from the vibration rod4239 to all the three process liquids, that is, the remover liquid, theorganic solvent and deionized water, on the substrate W. However, anyone or any two of the remover liquid, the organic solvent and thedeionized water on the substrate W may be subjected to ultrasonic wavesfrom the vibration rod 4239.

[0713] In each of the above-mentioned preferred embodiments, the holdingrotary section rotates the substrate while maintaining it horizontally.However, the holding rotary section may rotate the substrate with itsmajor surface being tilted with respect the horizontal surface, or mayrotate the substrate with its major surface being maintained in thevertical direction.

[0714] Moreover, in each of the above-mentioned preferred embodiments,the holding rotary section holds only one substrate. However, theholding rotary section may be designed to hold a plurality ofsubstrates.

[0715] In each of the above-mentioned preferred embodiments, thesubstrate treatment deals with a substrate having a surface on whichpolymers are formed through dry-etching. However, the present substratetreatment is more effectively applied to a substrate that has beenfurther subjected to ashing after the dry-etching.

[0716] Moreover, in each of the substrate processing apparatuses in therespective preferred embodiments, when the temperature-adjusting devicefor adjusting the temperature of the remover liquid sets the temperatureof the remover liquid to a temperature higher than room temperature(approximately, 25° C.), in particular, to not less than 60° C., it ispossible to obtain greater effects.

[0717] In other words, in the case when a remover liquid having atemperature higher than room temperature is supplied to the substrate,the remover liquid is easily cooled off. In the case when the removerliquid arrival point is fixed to a specific position on the substrate,although, at the specific position, the remover liquid having a propertemperature is supplied thereto to remove the reaction products with amaximum efficiency, the remover liquid is cooled off at the portionsother than the specific portion, failing to remove the reaction productswith a high efficiency.

[0718] However, in the substrate processing apparatuses in therespective preferred embodiments, since the arrival point of the removerliquid at the substrate W is shifted so that it becomes possible tosupply the remover liquid having a predetermined temperature to each ofthe portions on the substrate.

[0719] In particular, in the substrate processing apparatuses in therespective preferred embodiments, the substrate W is rotated, and thearrival point of the remover liquid with respect to the substrate W isallowed to shift on a line passing through the rotation center of thesubstrate and the circumference of a rotation circle that the end edgeof the substrate W forms when the substrate W rotates. This arrangementmakes it possible to supply the remover liquid having a predeterminedtemperature to all the portions of the substrate W, and consequently tooptimize the removing efficiency of the reaction products on the entireportions of the substrate W. Thus, it becomes possible to ensure thein-plane uniformity of the substrate W in the process.

[0720] (E. Preferred Embodiments According to Fifth Aspect of thePresent Invention)

[0721] <1. Substrate Processing Apparatus 5001>

[0722]FIGS. 49 and 50 are drawings that show the construction of asubstrate processing apparatus 5001. Here, FIG. 49 is a cross-sectionalview taken along line F49-F49 of FIG. 50, and for convenience ofexplanation, hatching is partially omitted from some portions.

[0723] As illustrated in FIG. 49, the substrate processing apparatus5001 is provided with a cup 5003 which has a virtually U-letter shape inits cross-section, and also has a virtually ring shape with an openingin the center portion thereof as shown in FIG. 50, when viewed fromabove, a holding rotary section 5005 that is formed in a manner so as tostick out through the opening of the cup 5003 in the vertical directionas shown in FIG. 49 and that rotates while holding a substrate W, aremover liquid supplying section 5007 for supplying a remover liquid tothe substrate W held by the holding rotary section 5005 and a deionizedwater supplying section 5009 for also supplying deionized water to thesubstrate W held by the holding rotary section 5005.

[0724] The cup 5003 has a plurality of discharging outlets 5004 on thebottom thereof. Thus, an excessive portion of the liquid supplied to thesubstrate W drops along the inner wall of the cup 5003 to reach thedischarging outlets 5004, and is discharged out of the apparatus throughthe discharging outlets 5004.

[0725] The holding rotary section 5005 is provided with a spin motor5013 which is secured to an apparatus frame, not shown, and has adriving shaft placed in the vertical direction, a spin shaft 5014 thatis secured to the driving shaft of the spin motor 5013 and a vacuumchuck 5015 serving as a substrate holding member placed on the top ofthe spin shaft 5014.

[0726] The vacuum chuck 5015 has a suction hole, not shown, formed in asuction surface that is a top major surface thereof, and air is suckedthrough the suction hole. Thus, the substrate W, placed on the vacuumchuck 5015, is held by air suction applied through the suction hole.

[0727] In this arrangement, the holding rotary section 5005 holds thesubstrate W placed on the vacuum chuck 5015 through suction applied bythe vacuum chuck 5015, and rotates the substrate W held on the vacuumchuck 5015 by driving the spin motor 5013.

[0728] The remover liquid supplying section 5007 is provided with afirst rotary motor 5017 which is secured to the apparatus frame, notshown, and has a driving shaft placed in the vertical direction, a firstrotary shaft 5019 secured to the driving shaft of the first rotary motor5017 and a first arm 5021 connected to the top of the first rotary shaft5019.

[0729] A remover liquid discharging nozzle 5011 is attached to the tipof the first arm 5021. The remover liquid discharging nozzle 5011 is atube-shaped member with its length direction set virtually in thevertical direction, and a remover liquid is supplied from one endthereof, with the other end supplying the remover liquid to thesubstrate W.

[0730] Moreover, a remover liquid injection nozzle 5012 is attached tothe same tip of the first arm 5021 through a bracket 5023 (indicated byan alternate long and two short dashes line in FIG. 50).

[0731] The remover liquid injection nozzle 5012, which sprays a removerliquid that is pressurized (hereinafter, also referred to as pressurizedremover liquid), as will be described later, is arranged so as to spraythe remover liquid with an inclination of 45 degrees with respect to thesurface of the substrate W.

[0732] Here, the above-mentioned remover liquid discharging nozzle 5011and remover liquid injection nozzle 5012 are arranged so that theremover liquid discharged from the remover liquid discharging nozzle5011 and the pressurized remover liquid sprayed from the remover liquidinjection nozzle 5012 are allowed to intersect each other on the surfaceof the substrate W, and so that, when the remover liquid dischargingnozzle 5011 and the remover liquid injection nozzle 5012 are allowed topivot by the first rotary motor 5017, the remover liquid discharged fromthe remover liquid discharging nozzle 5011 and the pressurized removerliquid sprayed from the remover liquid injection nozzle 5012 arereciprocally shifted, as illustrated in FIG. 50, on a circular arc 5085that passes through the rotation center C of the substrate W and alsointersects a rotation circle 5095 that the end edge of the rotatingsubstrate W forms at two points on the circumference thereof.

[0733] The deionized water supplying section 5009, which is secured tothe apparatus frame, not shown, is provided with a second rotary motor5031 having a driving shaft directed in the vertical direction, a secondrotary shaft 5033 secured to the driving shaft of the second rotarymotor 5031 and a second arm 5035 connected to the top of the secondrotary shaft 5033.

[0734] A deionized water discharging nozzle 5024 is attached to the tipof the second arm 5035. The deionized water discharging nozzle 5024 is atube-shaped member with its length direction set virtually in thevertical direction, and deionized water is supplied from one endthereof, with the other end supplying the deionized water to thesubstrate W.

[0735] Moreover, a deionized water injection nozzle 5025 is attached tothe same tip of the second arm 5035 through a bracket 5026 (indicated byan alternate two dots dash line in FIG. 50). The deionized waterinjection nozzle 5025, which sprays a deionized water mist that ispressurized (hereinafter, also referred to as pressurized deionizedwater), as will be described later, is arranged so as to spray thepressurized deionized water with an inclination of 45 degrees withrespect to the surface of the substrate W.

[0736] The above-mentioned deionized water discharging nozzle 5024 anddeionized water injection nozzle 5025 are arranged so that the deionizedwater discharged from the deionized water discharging nozzle 5024 andthe pressurized deionized water sprayed from the deionized waterinjection nozzle 5025 are allowed to intersect each other on the surfaceof the substrate W, and so that, when the deionized water dischargingnozzle 5024 and the deionized water injection nozzle 5025 are allowed topivot by the second rotary motor 5031, the deionized water dischargedfrom the deionized water discharging nozzle 5024 and the pressurizeddeionized water sprayed from the deionized water injection nozzle 5025are reciprocally shifted, as illustrated in FIG. 50, on a circular arc5087 that passes through the rotation center C of the substrate W andalso intersects a rotation circle 5095 that the end edge of the rotatingsubstrate W forms, at two points on the circumference thereof.

[0737] <2. Remover Liquid Supplying System, Deionized Water SupplyingSystem, Nitrogen Supplying System>

[0738]FIG. 51 shows a remover liquid supplying system 5089, a deionizedwater supplying system 5091 and a nitrogen supplying system 5093.

[0739] The remover liquid supplying system 5089 is provided with apressure pump 5065 for pumping the remover liquid from a remover liquidsource 5045 outside the apparatus, a filter 5061 for filteringcontaminants from the remover liquid pumped by the pressure pump 5065,and a remover liquid injection valve 5053 for opening and closing theflowing path of the filtered remover liquid to the remover liquidinjection nozzle 5012. Moreover, the remover liquid supplying system5089 is provided with a remover liquid pump 5047 for pumping the removerliquid from the remover liquid source 5045, a filter 5049 for filteringcontaminants from the remover liquid pumped by the remover liquid pump5047, and a remover liquid discharging valve 5056 for opening andclosing the flowing path of the filtered remover liquid to the removerliquid discharging nozzle 5011.

[0740] With this arrangement, the remover liquid supplying system 5089is allowed to supply the purified remover liquid to the remover liquidinjection nozzle 5012 and the remover liquid discharging nozzle 5011.

[0741] A remover liquid injection hole having a bore diameter of notmore than 0.5 mm, preferably, not more than 0.1 mm, is formed in the tipof the remover liquid injection nozzle 5012 so that the remover liquidpressure pump 5065 is allowed to discharge a high-pressure removerliquid from the remover liquid injection hole. In this case, the highpressure corresponds to a pressure that measures not less than 2.94×106Pa (30 kgf/cm²) upon arrival on the substrate W.

[0742] The deionized water supplying system 5091 is provided with adeionized water pressure pump 5066 for pumping deionized water from adeionized water source 5055 outside the apparatus, a filter 5064 forfiltering contaminants from the deionized water pumped by the deionizedwater pressure pump 5066, and a deionized water injection valve 5063 foropening and closing the flowing path of the filtered deionized water tothe deionized water injection nozzle 5025. Moreover, the deionized watersupplying system 5091 is provided with a deionized water pump 5057 forpumping deionized water from the deionized water source 5055, a filter5059 for filtering contaminants from the deionized water pumped by thedeionized water pump 5057, and a deionized water discharging valve 5056for opening and closing the flowing path of the filtered deionized waterto the deionized water injection nozzle 5024.

[0743] With this arrangement, the deionized water supplying system 5091is allowed to supply the purified deionized water to the deionized waterinjection nozzle 5025 and the deionized water discharging nozzle 5024.

[0744] A deionized water injection nozzle hole having a bore diameter ofnot more than 0.5 mm, preferably, not more than 0.1 mm, is formed in thetip of the deionized water injection nozzle 5025 so that the deionizedwater pressure pump 5066 is allowed to discharge a high-pressuredeionized water from the deionized water injection hole. In this case,the high pressure corresponds to a pressure that measures not less than2.94×106 Pa (30 kgf/cm²) upon arrival on the substrate W.

[0745] <3. Liquid Pressurizing Section>

[0746] The above-mentioned remover liquid pressure pump 5065 and thedeionized water pressure pump 5066 have the same structure in which apressure pump 5027, shown in FIG. 52, is used. The following descriptionwill discuss a liquid pressurizing section 5016 containing the pressurepump 5027. The liquid pressurizing section 5016 is provided with thepressure pump 5027, and an electromagnetic valve 5037 which switches thesupply end of air from a pressurized air source 5043 to a front port5029 or a rear port 5030, which will be described later, and which, whenthe supply end is the front port 5029, allows the rear port 5030 tocommunicate with an air-releasing section 5044 outside the apparatus soas to release air from the rear port 5030, and when the supply end isthe rear port 5030, allows the front port 5029 to communicate with theair-releasing section 5044 so as to release air from the front port5029.

[0747] The pressure pump 5027 is provided with a tube-shaped cylinder5028 with its front end closed and its rear end opened, a slidingchamber 5052 the front end of which is connected to the rear end of thecylinder 5028 in a sealed state with the rear end thereof being closed,and which has a column-shaped sliding space 5067 having a diameterlarger than the inner diameter of the cylinder 5028 inside thereof, apiston 5028P inserted into the cylinder 5028 so as to freely slidetherein, a sliding member 5071 that is connected to the piston 5028P andslides inside the sliding chamber 5052 so that the piston 5028P isallowed to slide on the cylinder 5028, the front port 5029 thatcommunicates with a space (front chamber 5092) on the side in which thepiston 5028P is placed of the sliding chambers 5067 divided by thesliding member 5071 and the rear port 5030 that communicates with aspace (rear chamber 5093) formed on the side opposite to the frontchamber of the sliding chambers 5067 divided by the sliding member 5071.Moreover, the cylinder 5028 and the front end of the piston 5028P form aspace (referred to as a liquid chamber 5083). Moreover, a flow inlet5074, which communicates with the liquid chamber 5083, is formed in thetip of the cylinder 5028 on the closed side so that a process liquidreleased from a process liquid source 5067 is allowed to flow from theflow inlet 5074 to the liquid chamber 5083 through a flow-in sidereverse stopping valve 5074. Moreover, a flow outlet 5082, whichcommunicates with the liquid chamber 5083, is formed in the tip of thecylinder 5028 on the closed side so that the process liquid inside theliquid chamber 5083 is allowed to flow out through a flow-out sidereverse stopping valve 5075.

[0748] In the liquid pressurizing section 5016 of this type, air issupplied from the pressurized air source 5043 to the front port 5029 byoperating the electromagnetic valve 5037. Then, since the air issupplied into the front chamber 5092, the sliding member 5071 is shiftedtoward a rear wall 5073. Thus, the piston 5028P is allowed to retreat sothat the process liquid is allowed to flow into the liquid chamber 5083.At this time, since the flow-out side reverse stopping valve 5075 isplaced in the flow outlet 5082, no liquid is flow in the liquid chamber5083 from the flow outlet 5082.

[0749] After a predetermined amount of the process liquid has beenstored in the liquid chamber, the electromagnetic valve 5037 is operatedso as to switch the supply end of air to the rear port 5030. Then, sinceair is supplied to the rear chamber 5093, the sliding member 5071 isshifted toward a rear wall 5072. Thus, the piston 5028P is allowed toadvance so that the process liquid inside the liquid chamber 5083 isallowed to flow out of the flow outlet 5082. At this time, since theflow-in side reverse stopping valve 5074 is placed in the flow inlet5081, no liquid is allowed to flow reversely from the liquid chamber5083 to the flow inlet 5081.

[0750] Thus, the liquid pressurizing section 5016 is allowed to flow thepressurized process liquid.

[0751] In the case when, the above-mentioned pressure pump 5027 isadopted as the remover liquid pressure pump 5065, the process liquidsource 5067 corresponds to the remover liquid source 5045. Here, thepressurized remover liquid flowing from the flow-out side reversestopping valve 5075 is sent toward the filter 5061.

[0752] Moreover, in the case when the pressure pump 5027 is adopted asthe deionized water pressure pump 5066, the process liquid source 5067corresponds to the deionized water source 5055. Here, the pressurizeddeionized water flowing from the flow-out side reverse stopping valve5075 is sent toward the filter 5064.

[0753] <4. Control Means>

[0754]FIG. 53 shows a control means 5069 of the substrate processingapparatus 5001.

[0755] The control means 5069 are connected to the spin motor 5013, thefirst rotary motor 5017, the second rotary motor 5031, the removerliquid pump 5047, the deionized water pump 5057, the remover liquidinjection valve 5053, the deionized water injection valve 5063, theremover liquid discharging valve 5056, the deionized water dischargingvalve 5058, the remover liquid side nitrogen valve 5066, the deionizedwater side nitrogen valve 5065, the temperature-adjusting device 5051and the temperature-adjusting device 5061. Thus, as will be described ina substrate processing method, the control means 5069 controls thesedevices connected thereto.

[0756] In the present substrate processing apparatus 5001, thegas-liquid mixing nozzle 5027 is adopted as the remover liquid injectionnozzle 5012 and the deionized water injection nozzle 5025. Since thegas-liquid mixing nozzle 5027 has a straight flow section 5037, it ispossible to regulate the remover liquid mist and the deionized watermist from dispersing. For this reason, the remover liquid mist and thedeionized water mist are accelerated to a predetermined velocity, andthe remover liquid mist and the deionized water mist are allowed toreach the substrate W with their velocity less attenuated.

[0757] In the present substrate processing apparatus 5001, the removerliquid mist and the deionized water mist from the remover liquidinjection nozzle 5012 and the deionized water injection nozzle 5025 aresprayed with an angle of 45 degrees with respect to the surface of thesubstrate W, and in general, they can be sprayed in a direction tiltedfrom the normal to the substrate W. In order to properly remove thereaction products of the side walls, the angle between the dischargingdirection of the remover liquid mist and the deionized water mist andthe surface of the substrate W is preferably set in the range of notless than 30 degrees to not more than 60 degrees, in particular, at 45degrees.

[0758] <5. Substrate Processing Method Using the Substrate ProcessingApparatus 5001>

[0759] As illustrated in FIG. 53, the present substrate processingmethod using the substrate processing apparatus 5001 includes a removerliquid supplying step s5001, a remover liquid spinning-off step s5002, adeionized water supplying step s5003, and a deionized water spinning-offstep s5004.

[0760] (1. Remover Liquid Supplying Step s5001)

[0761] First, the control means 5069 drives the spin motor 5013 so thatthe substrate W is being rotated at a predetermined number ofrevolutions.

[0762] Moreover, the control means 5069 drives to rotate the firstrotary motor 5017, and also rotates the remover liquid pump 5047 withthe remover liquid discharging valve 5058 being opened so that theremover liquid is supplied to the substrate W from the remover liquiddischarging nozzle 5011. Thus, the substrate W is supplied with acomparatively large amount of the remover liquid, with the result thatthe reaction products on the substrate W start to swell.

[0763] Next, after a lapse of a first predetermined time from the startof the remover liquid supply from the remover liquid discharging nozzle5011, the remover liquid discharging valve 5058 is closed to stop thesupply of the remover liquid from the remover liquid discharging nozzle5011, and the remover liquid pump 5047 is also stopped. Then, theremover liquid pressure pump 5065 is driven with the remover liquidinjection valve 5053 is opened so that the pressurized remover liquid isdischarged to the substrate W from the remover liquid injection nozzle5012. Thus, the pressurized remover liquid is blasted onto the reactionproducts that are swelling and softening. Thus, the pressurized removerliquid is firmly driven into the reaction products, thereby allowing thereaction products to further swell, and the swelled reaction productscome off the substrate W.

[0764] Moreover, since the remover liquid injection nozzle 5012discharges the pressurized remover liquid with an angle of 45 degreeswith respect to the substrate W, the pressurized remover liquid isallowed to reach the reaction products adhering to the irregular sidewalls of the substrate W without being weakened in its force against thereaction products. Consequently, it is possible to further acceleratethe swelling and coming off of the reaction products from the substrateW.

[0765] The first predetermined time is a period of time from the startof the supply of the remover liquid from the remover liquid dischargingnozzle 5011 to the time at which the reaction products on the substrateW start to swell by the remover liquid supplied from the remover liquiddischarging nozzle 5011, and this has been preliminarily found throughexperiments.

[0766] Then, the control means 5069 stops the driving operation of thefirst rotary motor 5017 with the remover liquid injection nozzle 5012having retreated from a position above the cup 5003. Moreover, thecontrol means 5069 closes the remover liquid injection valve 5053, andalso stops the driving operation of the remover liquid pressure pump5065 so as to stop the supply of the remover liquid from the removerliquid supplying section 5007.

[0767] (2. Remover Liquid Spinning-Off Step s5002)

[0768] Next, the control means 5069 stops the supply of the removerliquid to the substrate W, while it successively rotates the spin motor5013 so as to maintain the rotating state of the substrate W. Thus, aremover liquid spinning-off step s5002 is executed.

[0769] In this remover liquid spinning-off step s5002, the substrate Wis rotated at not less than 500 rpm, more preferably, in the range from1000 rpm to 4000 rpm.

[0770] Moreover, the time during which the rotation is maintained is setto not less than 1 second, preferably, in the range of 2 to 5 seconds.

[0771] In this manner, the rotating state of the substrate is maintainedwith the supply of the remover liquid being stopped with respect to thesubstrate W, the remover liquid on the substrate W is spun off from thesubstrate W by a centrifugal force.

[0772] (3. Deionized Water Supplying Step s5003)

[0773] After the remover liquid spinning-off process s5002, the controlmeans 5069 rotates the second rotary motor 5031, and also drives thedeionized water pump 5057 so as to supply deionized water from thedeionized water discharging nozzle 5024 with the deionized waterdischarging valve 5058 being open. Thus, the substrate W is suppliedwith a comparatively large amount of deionized water so that thereaction products that have swelled on the substrate W start to bewashed away.

[0774] Next, after a lapse of a second predetermined time from the startof the deionized water supply from the deionized water dischargingnozzle 5024, the deionized water discharging valve 5058 is closed tostop the supply of the deionized water from the deionized waterdischarging nozzle 5024, and the deionized water pump 5057 is alsoclosed. Then, the deionized water pressure pump 5066 is driven with thedeionized water injection valve 5063 being open so that the pressurizeddeionized water is discharged to the substrate W from the deionizedwater injection nozzle 5025. Thus, the accelerated deionized water isblasted onto the reaction products that are swelling and softening, withthe result that the reaction products come off the substrate W.

[0775] Moreover, since the deionized water injection nozzle 5025 spraysthe pressurized deionized water with an angle of 45 degrees with respectto the substrate W, the pressurized deionized water is allowed to reachthe reaction products adhering to the irregular side walls of thesubstrate W without being weakened in its force against the reactionproducts. Consequently, it is possible to further accelerate the comingoff of the reaction products from the substrate W.

[0776] Here, the second predetermined time is a period of time from thestart of the deionized water supply from the deionized water dischargingnozzle 5024 to the time at which the reaction products on the substrateW have come off to a certain degree by the deionized water, and this hasbeen preliminarily found through experiments.

[0777] Next, the control means 5069 stops the driving operation of thesecond rotary motor 5031 with the deionized water injection nozzle 5025having retreated from a position above the cup 5003. Moreover, thecontrol means 5069 closes the deionized water injection valve 5063, andalso stops the driving operation of the deionized water pressure pump5066 so as to stop the supply of the deionized water from the deionizedwater supplying section 5009.

[0778] (4. Deionized Water Spinning-Off Step s5004)

[0779] After the deionized water supplying step s5003, the control means5069 stops the supply of the deionized water to the substrate W, whileit successively rotates the spin motor 5013 so as to maintain therotating state of the substrate W. Thus, a deionized water spinning-offstep s5004 is executed.

[0780] In this manner, by supplying the remover liquid and deionizedwater to the substrate W, the reaction products are removed therefrom.

[0781] In accordance with the present substrate processing method, untilthe first predetermined time has elapsed since the start of the removerliquid supplying step s5001, the liquid-state remover liquid iscontinuously supplied from the remover liquid discharging nozzle 5011.However, after the lapse of the first predetermined time, thepressurized remover liquid is supplied from the remover liquid injectionnozzle 5012. Thus, in comparison with a case in which the liquid-stateremover liquid is continuously supplied from the remover liquiddischarging nozzle 5011 for the entire remover liquid supplying processs5001, it is possible to reduce the amount of consumption of the removerliquid. Moreover, since the high-speed pressurized remover liquid isdischarged from the remover liquid injection nozzle 5012, the timerequired for the swelling of the reaction products on the substrate Wand coming-off thereof from the substrate W is shortened, thereby makingit possible to improve the throughput.

[0782] Furthermore, until the second predetermined time has elapsedsince the start of the deionized water supplying step s5003, theliquid-state deionized water is continuously supplied from the deionizedwater discharging nozzle 5024. However, after the lapse of the secondpredetermined time, the pressurized deionized water is supplied from thedeionized water injection nozzle 5025. Thus, in comparison with a casein which the liquid-state deionized water is continuously supplied fromthe deionized water discharging nozzle 5024 for the entire deionizedwater supplying process s5003, it is possible to reduce the amount ofconsumption of the deionized water. Moreover, since the high-speedpressurized deionized water is discharged from the deionized waterinjection nozzle 5025, the time required for the coming-off of thereaction products from the substrate W is shortened, thereby making itpossible to improve the throughput.

[0783] In accordance with the present substrate processing method, atthe remover liquid spinning-off step s5002, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W becomes very little, or no longer exists. Therefore, in thecase when, in this state, the deionized water is supplied to thesubstrate W at the deionized water supplying step s5003, the amount ofthe remover liquid that comes to contact the deionized water becomesvery little or none, and therefore, even in the event of a pH shock,hardly any adverse effect is given to the substrate W, or no pH shockoccurs.

[0784] Moreover, in the present substrate processing method, until thefirst predetermined time has elapsed since the start of the removerliquid supplying process s5001, the liquid-state remover liquid issupplied from the remover liquid discharging nozzle 5011, and up to thetime immediately before the start of the remover liquid spinning-offprocess s5002 after the lapse of the first predetermined time, thepressurized remover liquid is sprayed onto the substrate W from theremover liquid injection nozzle 5012. However, instead of thisarrangement, the following method may be adopted.

[0785] In other words, the pressurized remover liquid may be suppliedfrom the remover liquid injection nozzle 5012 for the entire process ofthe remover liquid supplying process s5001. In this case, it is notnecessary to install the remover liquid discharging nozzle 5011 in thesubstrate processing apparatus 5001.

[0786] Moreover, until a predetermined time has elapsed after the startof the remover liquid supplying step s5001, the pressurized removerliquid may be supplied from the remover liquid injection nozzle 5012,and after the lapse of the predetermined time, the liquid-state removerliquid may be supplied from the remover liquid discharging nozzle 5011.

[0787] In the present substrate processing method, until the secondpredetermined time has elapsed since the start of the deionized watersupplying process s5003, the liquid-state deionized water is suppliedfrom the deionized water discharging nozzle 5024, and up to the timeimmediately after the deionized water spinning-off step s5004, thepressurized deionized water is sprayed onto the substrate W from thedeionized water injection nozzle 5025. However, instead of thisarrangement, the following method may be adopted.

[0788] In other words, the pressurized deionized water may be suppliedfrom the deionized water injection nozzle 5025 during the entiredeionized water supplying step s5003. In this case, it is not necessaryto install the deionized water discharging nozzle 5024 in the substrateprocessing apparatus 5001.

[0789] Moreover, until a predetermined time has elapsed from the startof the deionized water supplying step s5003, the pressurized deionizedwater may be supplied from the deionized water injection nozzle 5025,and after the lapse of the predetermined time, the liquid-statedeionized water may be supplied from the deionized water dischargingnozzle 5024.

[0790] <6. Substrate Processing Apparatus 5100>

[0791] Referring to FIGS. 55 and 56, an explanation will be given of asubstrate processing apparatus 5100. Here, FIG. 56 is a cross-sectionalview taken along line F56-F56 of FIG. 55 and, for convenience ofexplanation, hatching is omitted from some portions.

[0792] The substrate processing apparatus 5100 is provided with asolvent supplying section 5002 serving as an intermediate rinsesupplying section, in addition to the aforementioned substrateprocessing apparatus 5001. The substrate processing apparatus 5100 hasmany parts that are in common with the substrate processing section5001. Therefore, the same parts as the substrate processing apparatus5001 are indicated by the same reference numerals, and the descriptionthereof is omitted.

[0793] The substrate processing apparatus 5100 has the solvent supplyingsection 5002, and the solvent supplying section 5002, which is securedto the apparatus frame, not shown, is provided with a third rotary motor5018 having a driving shaft placed in the vertical direction, a thirdrotary shaft 5020 secured to the rotary shaft of the third rotary motor5018 and a third arm 5022 connected to the top of the third rotary shaft5020.

[0794] A solvent discharging nozzle 5040 is installed on the tip of thethird arm 5022. The solvent discharging nozzle 5040 is a tube-shapedmember with its length direction set virtually in the verticaldirection, and an organic solvent is supplied to one end thereof withthe other end supplying the organic solvent to the substrate W.

[0795] Moreover, a solvent injection nozzle 5039 is attached to the sametip of the third arm 5022 through a bracket 5041 (indicated by analternate long and two short dashes line in FIG. 56). The solventinjection nozzle 5039, which discharges an organic solvent that ispressurized (hereinafter, also referred to as pressurized solvent) aswill be described later, is arranged so as to spray the pressurizedsolvent with an inclination of 45 degrees with respect to the surface ofthe substrate W.

[0796] The above-mentioned solvent discharging nozzle 5040 and solventinjection nozzle 5039 are arranged so that the organic solventdischarged from the organic solvent discharging nozzle 5040 and thepressurized solvent discharged from the solvent injection nozzle 5039are allowed to intersect each other on the surface of the substrate W,and so that, when the solvent discharging nozzle 5040 and the solventinjection nozzle 5039 are allowed to pivot by the third rotary motor5018, the organic solvent discharged from the solvent discharging nozzle5040 and the pressurized solvent sprayed from the solvent injectionnozzle 5039 are reciprocally shifted, as illustrated in FIG. 56, on acircular arc 5086 that passes through the rotation center C of thesubstrate W and also intersects a rotation circle 5095 that the end edgeof the rotating substrate W forms at two points on the circumferencethereof.

[0797] <7. Solvent Supplying System>

[0798]FIG. 57 shows the solvent supplying system 5090.

[0799] The solvent supplying system 5090 is provided with a solventpressure pump 5076 for pumping the organic solvent from an organicsolvent source 5045 outside the apparatus, a filter 5032 for filteringcontaminants from the organic solvent that has been pumped by thesolvent pressure pump 5076, and a solvent injection valve 5054 foropening and closing the flowing path of the filtered organic solvent tothe solvent injection nozzle 5039. Moreover, the solvent supplyingsystem 5090 is also provided with a solvent pump 5048 for pumping theorganic solvent from the organic solvent source 5045, a filter 5052 forfiltering contaminants from the organic solvent pumped by the solventpump 5048, and a solvent discharging valve 5062 for opening and closingthe flowing path of the filtered organic solvent to the solventdischarging nozzle 5040.

[0800] With this arrangement, the solvent supplying system 5090 isallowed to supply the purified organic solvent to the solvent injectionnozzle 5039 and the solvent discharging nozzle 5040.

[0801] A solvent injection hole having a bore diameter of not more than0.5 mm, preferably, not more than 0.1 mm, is formed in the tip of thesolvent injection nozzle 5039 so that the solvent pressure pump 5076 isallowed to discharge a high-pressure solvent from the solvent injectionhole. In this case, the high pressure corresponds to a pressure thatmeasures not less than 2.94×106 Pa (30 kgf/cm²) upon arrival on thesubstrate W.

[0802] Moreover, in this case, the aforementioned pressure pump 5027 isadopted as the solvent pressure pump 5076. In this case, the processliquid source 5067 of FIG. 52 corresponds to the organic solvent source5046. Further, the pressurized solvent flowing from the flow-out sidereverse stopping valve 5075 is sent toward the filter 5032.

[0803] The substrate processing apparatus 5100 has a control means, notshown, and in the same manner as the control means 5069 of the substrateprocessing apparatus 5001, to the control means 5069 are connected thespin motor 5013, the first rotary motor 5017, the second rotary motor5031, the remover liquid pump 5047, the deionized water pump 5057, theremover liquid injection valve 5053, the deionized water injection valve5063, the remover liquid discharging valve 5056, the deionized waterdischarging valve 5058, the remover liquid pressure pump 5065 and thedeionized water pressure pump 5066, and to this are further connectedthe third rotary motor 5018, the solvent pump 5048, the solventinjection valve 5054, the solvent discharging valve 5062 and the solventpressure pump 5076.

[0804] In the present substrate processing apparatus 5100, the solventinjection nozzle 5039 discharges the pressurized solvent with an angleof 45 degrees with respect to the surface of the substrate W, and, inorder to properly remove the reaction products on side walls, the anglebetween the discharging direction of the pressurized solvent and thesurface of the substrate W is preferably set in the range of 30 degreesto 60 degrees, more preferably, at 45 degrees.

[0805] <8. Substrate Processing Method Using the Substrate ProcessingApparatus 5100>

[0806] Referring to FIG. 58, an explanation will be given of a substrateprocessing method in which the above-mentioned substrate processingapparatus 5100 is used.

[0807] The present substrate processing method using the substrateprocessing apparatus 5100 includes a remover liquid supplying steps5031, a remover liquid spinning-off step s5032, a solvent supplyingstep s5033 serving as an intermediate rinse process, a deionized watersupplying step s5034, and a deionized water spinning-off step s5035.

[0808] The present substrate processing method is virtually the same asthe substrate processing method using the substrate processing apparatus5001 having the remover liquid supplying step s5001, the remover liquidspinning-off step s5002, the deionized water supplying step s5003 andthe deionized water spinning-off step s5004, except that the solventsupplying step is interpolated between the remover liquid spinning-offstep s5002 and the deionized water supplying step s5003.

[0809] Therefore, the above-mentioned remover liquid supplying steps5031, the remover liquid spinning-off step s5032, the deionized watersupplying step s5034 and the deionized water spinning-off step s5035 arerespectively the same as the remover liquid supplying step s5001, theremover liquid spinning-off step s5002, the deionized water supplyingstep s5003 and the deionized water spinning-off step s5004 in thesubstrate processing method using the substrate processing apparatus5001, and therefore, the description thereof is omitted.

[0810] The following description will discuss the solvent supplyingprocess s5033.

[0811] The solvent supplying step s5033 is carried out after the removerliquid supplying step s5031 and the remover liquid spinning-off steps5032 have been finished. In the remover liquid spinning-off step s5032,the substrate is kept rotating with the supply of the remover liquid tothe substrate W being stopped so that the remover liquid on thesubstrate W is spun off from the substrate W by a centrifugal force.Thus, the remover liquid remaining on the substrate W is reduced to aminimum.

[0812] At the time of the start of the solvent supplying process s5033,the control means, not shown, rotates the third rotary motor 5018, andalso drives the solvent pump 5048 so as to supply the organic solventfrom the solvent discharging nozzle 5040, with the solvent dischargingvalve 5062 being opened. Thus, the substrate W is supplied with acomparatively large amount of the organic solvent so that the removerliquid on the substrate W starts to be washed away.

[0813] Next, after a lapse of a third predetermined time from the startof the solvent supplying step s5033, the solvent discharging valve 5062is closed so that the supply of the organic solvent from the solventdischarging nozzle 5040 is stopped, and the solvent pump 5048 that hasbeen driven is also stopped. Then, after the lapse of the thirdpredetermined time, the solvent pressure pump 5076 is driven with thesolvent injection valve 5054 being opened so that the pressurizedsolvent from the solvent injection nozzle 5039 is sprayed on thesubstrate W. Thus, the highly pressurized solvent is sprayed onto thereaction products that have swelled and softened, with the result thatthe reaction products come off from the substrate W.

[0814] Moreover, since the solvent injection nozzle 5039 sprays thepressurized solvent with an angle of 45 degrees with respect to thesubstrate W, the pressurized solvent is allowed to reach the reactionproducts adhering to the irregular side walls of the substrate W withoutbeing weakened in its force against the reaction products. Consequently,it is possible to further accelerate the swelling and coming-off of thereaction products from the substrate W. Thus, it becomes possible toshorten the time required for the process.

[0815] The third predetermined time is a period of time from the startof the solvent supplying step s5033 to the time at which the removerliquid on the substrate W has been washed away to a certain degree bythe organic solvent supplied from the solvent discharging nozzle 5040,and this has been preliminarily found through experiments.

[0816] Then, immediately before the deionized water supplying processs5034, the control means, not shown, stops the driving operation of thethird rotary motor 5018 with the solvent injection nozzle 5039 havingretreated from a position above the cup 5003. Moreover, the controlmeans, not shown, closes the solvent injection valve 5054 and also stopsthe solvent pressure pump 5076 so as to stop the supply of the organicsolvent from the solvent supplying section 5002.

[0817] In this manner, in the solvent supplying step s5033, the organicsolvent is supplied to the substrate W so that the remover liquid iswashed away from the substrate W. For this reason, even when deionizedwater is supplied to the substrate W in the succeeding deionized watersupplying step s5034, no remover liquid contacting the deionized waterexists, thereby making it possible to prevent the occurrence of a pHshock. Consequently, it is possible to prevent the resulting damages tothe thin films on the substrate W.

[0818] In accordance with the present substrate processing method, atthe remover liquid spinning-off step s5032, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W at this point of time is very little. For this reason, it ispossible to shorten the time required for the organic solvent to removethe remover liquid at the solvent supplying step s5033. Thus, it ispossible to improve the throughput. In the same manner, since theremover liquid remaining on the substrate W is very little, it ispossible to reduce the amount of the organic solvent required for thesolvent supplying process s5033, and consequently to reduce the costs.

[0819] In the present substrate processing method, immediately after thesolvent supplying step s5033, the deionized water supplying processs5034 is executed. However, a solvent spinning-off step for spinning thesolvent off from the substrate W may be interpolated between the solventsupplying step s5033 and the deionized water supplying step s5034.

[0820] Moreover, in the present substrate processing method, therotation of the substrate W has not been stopped from the start of theremover liquid supplying step s5031 to the completion of the deionizedwater spinning-off step s5035. However, the rotation of the substrate Wmay be stopped in any one of the intervals between the remover liquidsupplying step s5031 and the remover liquid spinning-off step s5032,between the remover liquid spinning-off step s5032 and the solventsupplying step s5033, between the solvent supplying step s5033 and thedeionized water supplying step s5034, and between the deionized watersupplying step s5034 and the deionized water spinning-off process s5035.

[0821] In the present substrate processing method, until the firstpredetermined time has elapsed since the start of the remover liquidsupplying step s5031, the liquid-state remover liquid is supplied fromthe remover liquid discharging nozzle 5011, and up to the timeimmediately before the start of the remover liquid spinning-off steps5032 after the lapse of the first predetermined time, the pressurizedremover liquid is sprayed onto the substrate W from the remover liquidinjection nozzle 5012. However, instead of this arrangement, thefollowing method may be adopted.

[0822] In other words, the pressurized remover liquid may be suppliedfrom the remover liquid injection nozzle 5012 during the entire removerliquid supplying process s5031. In this case, it is not necessary toinstall the remover liquid discharging nozzle 5011 in the substrateprocessing apparatus 5001.

[0823] Until a predetermined time has elapsed from the start of theremover liquid supplying step s5031, the pressurized remover liquid maybe supplied from the remover liquid injection nozzle 5012, and after thelapse of the predetermined time, the liquid-state remover liquid may besupplied from the remover liquid discharging nozzle 5011.

[0824] Moreover, in the present substrate processing method, until thethird predetermined time has elapsed since the start of the solventsupplying step s5033, the liquid-state organic solvent is supplied fromthe solvent discharging nozzle 5040, and up to the time immediatelybefore the start of the deionized water supplying process s5034 afterthe lapse of the third predetermined time, the pressurized solvent issprayed onto the substrate W from the solvent injection nozzle 5039.However, instead of this arrangement, the following method may beadopted.

[0825] In other words, the pressurized solvent may be supplied from thesolvent injection nozzle 5039 during the entire solvent supplying steps5033. In this case, it is not necessary to install the solventdischarging nozzle 5040 in the substrate processing apparatus 5100.

[0826] Further, until a predetermined time has elapsed since the startof the solvent supplying step s5033, the pressurized solvent may besupplied from the solvent injection nozzle 5039, and up to the timeimmediately before the deionized water supplying process s5034 after thelapse of the predetermined time, the liquid-state organic solvent may besupplied from the solvent discharging nozzle 5040.

[0827] In the present substrate processing method, until the secondpredetermined time has elapsed since the start of the deionized watersupplying process s5033, the liquid-state deionized water is suppliedfrom the deionized water discharging nozzle 5024, and up to the timeimmediately before the deionized water spinning-off step s5004 after thelapse of the second predetermined time, the pressurized deionized wateris sprayed onto the substrate W from the deionized water injectionnozzle 5025. However, instead of this arrangement, the following methodmay be adopted.

[0828] In other words, the pressurized deionized water may be suppliedfrom the deionized water injection nozzle 5025 during the entiredeionized water supplying process s5033. In this case, it is notnecessary to install the deionized water discharging nozzle 5024 in thesubstrate processing apparatus 5001.

[0829] Moreover, until a predetermined time has elapsed from the startof the deionized water supplying process s5033, the pressurizeddeionized water may be supplied from the deionized water injectionnozzle 5025, and after the lapse of the predetermined time, theliquid-state deionized water may be supplied from the deionized waterdischarging nozzle 5024.

[0830] <9. Supplementary>

[0831] In the above-mentioned substrate processing apparatuses 5001,5100, the holding rotary section rotates the substrate while maintainingit horizontally. However, the holding rotary section may rotate thesubstrate with its major surface being tilted with respect thehorizontal surface, or may rotate the substrate with its major surfacebeing maintained in the vertical direction.

[0832] Moreover, in the above-mentioned substrate processing apparatuses5001, 5100, the holding rotary section holds only one substrate.However, the holding rotary section may be designed to hold a pluralityof substrates.

[0833] In the substrate processing apparatus 5001, the remover liquidsupplying section 5007 is provided with the remover liquid injectionnozzle 5012 and the deionized water supplying section 5009 is providedwith the deionized water injection nozzle 5025 respectively. However,either the remover liquid injection nozzle 5012 or the deionized waterinjection nozzle 5025 may be omitted.

[0834] In the substrate processing apparatus 5100, the remover liquidsupplying section 5007 is provided with the remover liquid injectionnozzle 5012, the deionized water supplying section 5009 is provided withthe deionized water injection nozzle 5025 and the solvent supplyingsection 5002 is provided with the solvent injection nozzle 5039respectively. However, any one or any two of the remover liquidinjection nozzle 5012, the deionized water injection nozzle 5025 and thesolvent injection nozzle 5039 may be omitted.

[0835] Furthermore, in the present aspect, the substrate treatment dealswith a substrate having a surface on which polymers are formed throughdry-etching. However, the present substrate treatment is moreeffectively applied to a substrate that has been further subjected toashing after the dry-etching.

[0836] In the above-mentioned substrate processing apparatuses 5001,5100, even in the case when the reaction products are accumulated on thesubstrate W in a protruding form, the process liquid mist is dischargedonto the substrate W in a direction tilted with respect to the substrateW so that the reaction products, accumulated in the protruding form, isbroken by the process liquid mist. For this reason, it is possible tofinish the removing process of the reaction products more quickly.

[0837] Moreover, in the above-mentioned substrate processing apparatuses5001, 5100, the pressure pump 5027 is used in the liquid pressurizingsection for discharging a high-pressure process liquid from the removerliquid injection nozzle 5012, the deionized water injection nozzle 5025and the solvent injection nozzle 5039. However, instead of this, thefollowing arrangement may be used.

[0838] In other words, a sealed container storing the process liquid, apressurized gas supplying means for supplying pressurized gas into aspace within the sealed container, and a process liquid supplying tubewith its one end contacting the process liquid inside the sealedcontainer and the other end directed to the outside of the sealedcontainer are installed, and the process liquid may be supplied to theremover liquid injection nozzle 5012, the deionized water injectionnozzle 5025 or the solvent injection nozzle 5039 from the processingliquid supplying tube. With respect to gas used in this case, an inertgas is preferably used in order to prevent denature of the processliquid, and examples of the inert gas include nitrogen and argon.

[0839] (F. Preferred Embodiments According to Sixth Aspect of thePresent Invention)

[0840] <1. Substrate Processing Apparatus 5001>

[0841]FIG. 59 is a schematic drawing that shows a substrate processingapparatus in accordance with a preferred embodiment in the sixth aspectof the present invention.

[0842] This substrate processing apparatus is provided with a substrateprocessing section 6002, a temperature adjusting vessel 6003, atemperature adjusting mechanism 6004 and a remover liquid collectingsystem 6005. The temperature adjusting vessel 6003 is placed inside achemical cabinet 6100. Moreover, the substrate processing section isplaced inside a processing cabinet 6200. The temperature adjustingmechanism 6004 and the remover liquid collecting mechanism 6005 arearranged in association with the chemical cabinet 6100 and theprocessing cabinet 6200.

[0843] The substrate processing section 6002, which is used forsupplying a remover liquid for removing the reaction products to asurface of a substrate W so as to process the surface thereof, isprovided with a spin chuck 6023 that is allowed to rotate with thesubstrate W held thereon by the driving operation of the motor 6022, aremover liquid supplying nozzle 6021 for discharging the remover liquidonto the surface of the rotating substrate W, a remover liquid supplyingtube 6025 for connecting an electromagnetic valve 6044 to the removerliquid nozzle 6021, a scattering preventive cup 6024 for the removerliquid and a remover liquid collecting pot 6026.

[0844] In this substrate processing section 6002, the remover liquid,which has been temperature-controlled in the temperature adjustingvessel 6003, is supplied from the remover liquid supplying nozzle 6021onto the surface of the substrate W that is held on the spin chuck 6023and rotated, by opening the electromagnetic valve 6044. The reactionproducts, such as polymers accumulated on side walls of metal films onthe surface of the substrate W, are removed by the remover liquidsupplied from the remover liquid supplying nozzle 6021.

[0845] The temperature adjusting vessel 6003 stores the remover liquidto be supplied to the substrate W in the substrate processing section6002. The remover liquid is supplied to the temperature adjusting vessel6003 from a supplying section 6010 for the remover liquid.

[0846] The temperature adjusting mechanism 6004, which is used forheating the remover liquid inside the temperature adjusting vessel 6003,is provided with a heater 6042, a circulating pump 6041, a circulationpath 6043 for circulating the remover liquid inside the chemical cabinet6100 and a circulation path 6045 for circulating the remover liquid fromthe chemical cabinet 6100 to the processing cabinet 6200. The removerliquid inside the temperature adjusting vessel 6003 is heated to apredetermined temperature by the function of the heater 6042 while it iscirculated through the circulation paths 6043 and 6045 by the drivingoperation of the circulating pump 6004.

[0847] The remover liquid collecting mechanism 6005 is provided with aremover liquid collecting path 6011 for collecting the remover liquidthat has been used in the process for the substrate W and captured bythe scattering preventive cup 6024 and the remover liquid that has beendischarged from the remover liquid supplying nozzle 6021 toward theremover liquid collecting pot 6026, a remover liquid storing vessel 6029for temporarily storing the remover liquid collected through the removerliquid collecting path 6011 and a pump 6027 used for collecting theremover liquid temporarily stored inside the remover liquid storingvessel 6029 through a tube path 6028.

[0848]FIG. 60 is a schematic side view that shows the construction ofthe above-mentioned substrate processing section 6002 including theremover liquid storing vessel 6029, etc., and FIG. 61 is a plan viewthat shows the construction of the substrate processing section 6002.Here, in FIG. 61, some portions of the substrate processing section 6002are indicated by cross-sectional views.

[0849] The scattering preventive cup 6024 for the remover liquid has avirtually U-letter shape in its cross-section, and also has a virtuallyring shape having an opening in its center portion, when viewed fromabove. An opening 6013, connected to the remover liquid collecting path6011, is formed in the bottom surface of the scattering preventive cup6024. The remover liquid collecting pot 6026 has a cylinder shape withits upper portion being open. Further, an opening 6012, connected to theremover liquid collecting path 6011, is formed in the bottom surface ofthe remover liquid collecting pot 6026.

[0850] The remover liquid supplying nozzle 6021, which serves as aremover liquid discharging section for discharging the remover liquidonto the surface of the substrate W, is attached to the tip of an arm6014 that is allowed to freely pivot centered on a shaft 6015 by thedriving operation of a motor 6016 shown in FIG. 61. Thus, the removerliquid supplying nozzle 6021 is allowed to reciprocally shift between asupplying position indicated by a solid line, shown in FIGS. 60 and 61,and a stand-by position indicated by an alternate long and two shortdashes line shown in FIGS. 60 and 61, by the driving operation of themotor 6016.

[0851] In this case, the supplying position is a position at which theremover liquid supplying nozzle 6021 is allowed to face the rotationcenter of the rotating substrate W that is held by the spin chuck 6023so that the remover liquid, discharged from the remover liquid supplyingnozzle 6023, is discharged onto the surface of the substrate W.Moreover, the above-mentioned stand-by position is a position at whichthe remover liquid supplying nozzle 6021 is allowed to face the removerliquid collecting pot 6026 so that the remover liquid, discharged fromthe remover liquid supplying nozzle 6021, is injected into the removerliquid collecting pot 6026.

[0852]FIG. 62 is a block diagram that shows an essential electricalconstruction of the substrate processing apparatus.

[0853] The substrate processing apparatus is provided with a controlsection 6050 having a CPU 6051 for executing logical operations, a ROM6052 in which operation programs required for the control of theapparatus are stored and a RAM 6053 in which data, etc., are temporarilystored at the time of the controlling operation. This control section6050 is connected to the motor 6016 used for reciprocally moving theremover liquid supplying nozzle 6021 between the supplying position andthe stand-by position, a motor 6022 for rotating the spin chuck 6023that is holding the substrate W, and the electromagnetic valve 6044 fordischarging the remover liquid from the remover liquid supplying nozzle6021, through an interface 6054.

[0854] Next, an explanation will be given of a processing operation inwhich the removing process for the reaction products is carried out bythe above-mentioned substrate processing apparatus.

[0855] In the above-mentioned substrate processing apparatus, theremover liquid inside the remover liquid supplying tube 6025, whichreaches the remover liquid supplying nozzle 6021 from theelectromagnetic valve 6044, is not circulated. For this reason, during anon-processing period of time from the finish of the process forsubstrates in the first lot to the start of the process for substrates Win the next lot, the temperature of the remover liquid inside theremover liquid supplying tube 6025 becomes lower than the predeterminedtemperature. For this reason, in the substrate processing apparatus inaccordance with the present preferred embodiment, the following twoprocesses are carried out: a pre-dispensing process in which, prior tothe discharge of the remover liquid to the substrate W, the removerliquid is discharged from the remover liquid supplying nozzle 6021 tothe remover liquid collecting pot 6026 at the stand-by position and anauto-dispensing process in which, during the non-processing period ofthe substrate W, the remover liquid is intermittently discharged fromthe remover liquid supplying nozzle 6021 to the remover liquidcollecting pot 6026 at the stand-by position.

[0856]FIG. 63 is a flow chart that shows the processing operation in thesubstrate processing apparatus at the time of the pre-dispensingoperation. Moreover, FIG. 64 is a flow chart showing the processingoperation in the substrate processing apparatus at the time of theauto-dispensing operation, which forms a sub-routine of the flow chartshown in FIG. 63.

[0857] As shown in the flow chart of FIG. 63, at the time when theremoving process of the reaction products is executed by using thesubstrate processing apparatus, first, the execution flow for theauto-dispensing process shown in FIG. 64 is started as a sub-routine(step S6011). Here, the operation of the auto-dispensing process will bedescribed later.

[0858] Next, a determination is made as to whether or not the substratesW in the first lot have been carried in (step S6012).

[0859] When the substrates W in the first lot have been carried in, thepre-dispensing process is carried out (step S6013). At the time when thepre-dispensing process is executed, the electromagnetic valve 6044 isopened with the remover liquid supplying nozzle 6021 having been movedto the stand-by position indicated by the alternate long and two shortdashes line in FIGS. 60 and 61. Thus, the pressurized remover liquid,which is circulated inside the circulating path 6045, is discharged fromthe remover liquid discharging nozzle 6021. The remover liquid,discharged from the remover liquid discharging nozzle 6021, istemporarily stored in the remover liquid storing vessel 6029 through theremover liquid collecting pot 6026 and the remover liquid collectingpath 6011, and then collected by the temperature adjusting vessel 6003by the function of the pump 6027.

[0860] By executing the pre-dispensing process, the remover liquidinside the remover liquid supplying tube 6025 from the electromagneticvalve 6044 to the remover liquid supplying nozzle 6021, which is notcirculated in the normal state and is lower than the set temperature, isdischarged so that the remover liquid, which is always circulated andheated to the set temperature, is newly introduced into the removerliquid supplying tube 6025. In this case, during the pre-dispensingprocess, for example, the remover liquid may be continuously dischargedfor approximately 15 seconds, although it depends on the length of theremover liquid supplying tube 6025, etc.

[0861] In this state, the substrates W in the first lot are subjected tothe process (step S6014). At the time of carrying out the process on thesubstrates W, the substrate W is rotated at a high-speed by the spinchuck 6023, and the electromagnetic valve 6044 is opened with theremover liquid supplying nozzle 6021 being set at the supplying positionindicated by the solid line shown in FIGS. 60 and 61. Thus, thepressurized remover liquid, which is being circulated in the circulationpath 6045, is discharged from the remover liquid discharging nozzle6021. At the time of this process of the substrate W, the substrate W istreated by the remover liquid that has been initially heated to the settemperature. For this reason, it is possible to execute the removingprocess of the reaction products with high precision.

[0862] Upon completion of the process of the substrates W in the firstlot, the sequence is set to a stand-by state until substrates W in a lotto be processed next have been carried in (step S6015). In this stand-bystate, the auto-dispensing process, shown in FIG. 64 as the sub-routine,is carried out.

[0863] In other words, a determination is made as to whether or not apredetermined period of time has elapsed since the completion of theprocessing step (step S6014) of the substrate W (step S6021).

[0864] Then, after the predetermined time has elapsed, theauto-dispensing process is carried out (step S6022). At the time whenthe auto-dispensing process is executed, in the same manner as theabove-mentioned pre-dispensing process, the electromagnetic valve 6044is opened with the remover liquid supplying nozzle 6021 being set at thestand-by position indicated by the alternate long and two short dashesline in FIGS. 60 and 61. Thus, the pressurized remover liquid, which isbeing circulated through the circulation path 6045, is discharged fromthe remover liquid discharging nozzle 6021. The remover liquid,discharged from the remover liquid discharging nozzle 6021, istemporarily stored in the remover liquid storing vessel 6029 through theremover liquid collecting pot 6026 and the remover liquid collectingpath 6011, and then collected in the temperature adjusting vessel 6003by the function of the pump 6027.

[0865] The auto-dispensing process is carried out every fixed time, thatis, in an intermittent manner. Thus, the remover liquid inside theremover liquid supplying tube 6025 from the electromagnetic valve 6044to the remover liquid supplying nozzle 6021, which is not circulated inthe normal state and is lower than the set temperature, is discharged sothat the remover liquid, which is always circulated and heated to theset temperature, is newly introduced into the remover liquid supplyingtube 6025.

[0866] In the case when the remover liquid is held inside the removerliquid supplying tube 6025 for a long time, not only the remover liquidinside the remover liquid supplying tube 6025, but also the removerliquid supplying tube 6025 has a low temperature. Therefore, even whenthe above-mentioned pre-dispensing process is carried out, thetemperature of the remover liquid to be first supplied to the substrateW might become lower than the set temperature. However, theabove-mentioned auto-dispensing process is carried out so that itbecomes possible to prevent the occurrence of this phenomenonbeforehand. Here, during the pre-dispensing process, for example, theremover liquid may be continuously discharged for approximately 15seconds once every hour.

[0867] As also shown in FIG. 63, in the case when all the processes onthe substrate W have been completed (step S6015), after completion ofthe execution flow of the auto-dispensing process shown in FIG. 64 asthe sub-routine (step S6016), the entire processes are completed.

[0868] In the substrate processing apparatus in accordance with thepresent aspect, the pre-dispensing process is executed every timesubstrates W in a new lot have been carried in. However, thepre-dispensing process may be carried out every time a single substrateW is processed.

[0869] Moreover, in the substrate processing apparatus in accordancewith the present aspect, the auto-dispensing process is carried outevery fixed time, that is, in an intermittent manner. However, theauto-dispensing process may be carried out continuously. In other words,in the state where the substrate W has not been processed, the removerliquid supplying nozzle 6021 is set in the stand-by position indicatedby the alternate long and two short dashes line in FIGS. 60 and 61, andthe remover liquid may be continuously discharged toward the removerliquid collecting pot 6026 from the remover liquid nozzle 6021. In thiscase, it is preferable to set the flow of the remover liquid to bedischarged from the remover liquid discharging nozzle smaller.

[0870] Moreover, in the substrate processing apparatus in accordancewith the above-mentioned preferred embodiment, both of theauto-dispensing process and the pre-dispensing process are executed inparallel with each other. However, either one of these may be executed.

[0871] In the substrate processing apparatus in accordance with theabove-mentioned preferred embodiment, the supplying position of theremover liquid supplying nozzle 6021 is determined as a position atwhich the remover liquid supplying nozzle 6021 is allowed to face therotation center of the substrate W. However, any position may be set asthe supplying position, as long as the remover liquid supplying nozzle6021 can supply the remover liquid to the substrate W. In the case ofthe substrate processing apparatus of the present aspect, for example,any position may be set as long as it allows the remover liquidsupplying nozzle 6021 to face the substrate W.

[0872] Further, in the substrate processing apparatus in accordance withthe present aspect, the stand-by position of the remover liquidsupplying nozzle 6021 is determined as a position at which the removerliquid supplying nozzle 6021 is allowed to face the remover liquidcollecting pot 6026. However, any position may be set as the stand-byposition, as long as the remover liquid supplying nozzle 6021 candischarge the remover liquid to the remover liquid collecting pot 6026.

[0873] Moreover, in the substrate processing apparatus in accordancewith the present aspect, the remover liquid supplying nozzle 6021discharges the remover liquid while it is stationed at a position atwhich the remover liquid supplying nozzle 6021 is allowed to face therotation center of the rotating substrate W. However, the arm 6014 isreciprocally rotated by the motor 6016 so that the remover liquid may bedischarged while the remover liquid nozzle 6021 is being shifted on acircular arc that passes through the rotation center of the substrate Wand the circumferential edge of the substrate W.

[0874] (G. Preferred Embodiments According to Seventh Aspect of thePresent Invention)

[0875] The following description will discuss the construction of asubstrate processing apparatus in accordance with a seventh aspect ofthe present invention. Here, this substrate processing apparatus is usedfor removing polymers from a surface of a silicon semiconductor waferserving as a substrate having a thin film formed thereon, the polymershaving been generated on the surface as reaction products.

[0876]FIG. 65 is a schematic plan view that shows a substrate processingapparatus in accordance with a first preferred embodiment of the seventhaspect. Moreover, FIGS. 66 to 68 are schematic side views that show thesubstrate processing apparatus in accordance with the first preferredembodiment of the seventh aspect. Here, FIG. 66 shows the relationshipamong a remover liquid supplying mechanism 7030, a spin chuck 7070 and ascattering preventive cup 7073, FIG. 67 shows the relationship among abrush cleaning mechanism 7040, the spin chuck 7070 and the scatteringpreventive cup 7073, and FIG. 68 shows the relationship among adeionized water supplying mechanism 7050, the spin chuck 7070 and thescattering preventive cup 7073, and in these drawings, the scatteringpreventive cup 7073 and a back surface cleaning nozzle 7074 are shown intheir cross-sectional views.

[0877] This substrate processing apparatus is provided with the spinchuck 7070 serving as a rotation holding means for holding the substrateW so as to freely rotate thereon, a remover liquid supplying mechanism7030 for supplying a remover liquid toward the surface of the substrateW held on the spin chuck 7070 a brush cleaning mechanism 7040 forcleaning the surface of the substrate W held on the spin chuck 7070 witha rotary brush 7041, and a deionized water supplying mechanism 7050 forsupplying deionized water to the surface of the substrate W held on thespin chuck 7070.

[0878] As illustrated in FIGS. 66 to 68, the spin chuck 7070 is allowedto rotate centered on a support shaft 7072 directed in the verticaldirection by the driving operation of the motor 7071, with the substrateW being sucked thereon. Thus, the substrate W is allowed to rotatetogether with the spin chuck 7070 within a plane in parallel with itsmajor surface.

[0879] The scattering preventive cup 7073 is placed on the periphery ofthe spin chuck 7070. The scattering preventive cup 7073 has a virtuallyU-letter shape in its cross-section, and also has a virtually ring shapehaving an opening in its center portion, when viewed from above. Anopening 7075, connected to a drain not shown, is formed in the bottomsurface of the scattering preventive cup 7073.

[0880] Here, a back surface cleaning nozzle 7074 for cleaning the backsurface of the substrate W by supplying deionized water to the backsurface of the substrate W is placed at a position facing the backsurface of the substrate W in the scattering preventive cup 7073. Thisback surface cleaning nozzle 7074 is connected to a supply section 7057of deionized water through an electromagnetic valve 7076. Thus, thissupply section 7057 of deionized water is capable of sending pressurizeddeionized water.

[0881] As illustrated in FIG. 66, the remover liquid supplying mechanism7030 is provided with a remover liquid discharging nozzle 7031 fordischarging a remover liquid toward the substrate W. This remover liquiddischarging nozzle 7031 is attached to the tip of an arm 7034 that isallowed to freely pivot centered on a shaft 7033 directed in thevertical direction by the driving operation of a nozzle shiftingmechanism 7032. Thus, the remover liquid discharging nozzle 7031 isallowed to reciprocally shift between a position facing the rotationcenter of the rotating substrate W held on the spin chuck 7070 and aposition facing the end edge of the substrate W. Here, the nozzleshifting mechanism 7032 also has an arrangement for shifting the arm7034 in the vertical directions.

[0882] Moreover, the remover liquid discharging nozzle 7031 is connectedto a remover liquid supplying section 7037 through an electromagneticvalve 7036. The remover liquid supplying section 7037 has an arrangementcapable of sending a pressurized remover liquid that has been heated toa predetermined temperature. Here, reference numeral 7035 represents atube for supplying the remover liquid.

[0883] As illustrated in FIG. 67, the brush cleaning mechanism 7040 hasa rotary brush 7041 for cleaning the surface of the substrate W. Thisrotary brush 7041 is attached to the tip of an arm 7044 that is allowedto rock centered on a shaft 7043 directed in the vertical direction bythe driving operation of a rotary brush shifting mechanism 7042. Thus,the rotary brush 7041 is allowed to reciprocally shift between aposition facing the rotation center of the rotating substrate W held onthe spin chuck 7070 and a position facing the end edge of the substrateW. Here, the rotary brush shifting mechanism 7042 also has anarrangement for shifting the arm 7044 in the vertical direction.

[0884] The rotary brush 7041 is allowed to rotate, centered on a rotaryshaft 7045 directed in the vertical direction by the driving operationof the motor 7046 placed at the tip of the arm 7044. Moreover, asillustrated in FIG. 67, the lower end of the rotary brush 7041 can beshifted to a position for allowing it to contact the surface of thesubstrate W held on the spin chuck 7070 or a position that is apart fromthe surface of the substrate W held on the spin chuck 7070 with a finegap. In this arrangement, the arm 7044 is moved so as to reciprocallyshift the rotary brush 7041 between the position facing the rotationcenter of the rotating substrate W held on the spin chuck 7070 and theposition facing the end edge of the substrate W, with the rotary brush7041 being rotated at such a position. Thus, it is possible to clean theentire surface of the substrate W with the rotary brush 7041.

[0885] As illustrated in FIGS. 65 and 67, a deionized water injectionnozzle 7047, which supplies deionized water on the surface of thesubstrate W at the time of cleaning the substrate W using the rotarybrush 7041, is placed at a position facing the brush cleaning mechanism7041. This deionized water injection nozzle 7047 is connected to thedeionized water supplying section 7057 through an electromagnetic valve7048.

[0886] As illustrated in FIG. 68, the deionized water supplyingmechanism 7050 is provided with a deionized water discharging nozzle7051 for discharging deionized water toward the substrate W. Thisdeionized water discharging nozzle 7051 is attached to the tip of an arm7054 that is allowed to rock centered on a shaft 7053 directed in thevertical direction, by the driving operation of a nozzle shiftingmechanism 7052. Thus, the deionized water discharging nozzle 7051 isallowed to reciprocally shift between a position facing the rotationcenter of the rotating substrate W held on the spin chuck 7070 and aposition facing the end edge of the substrate W. Here, the nozzleshifting mechanism 7052 also has an arrangement for shifting the arm7044 in the vertical direction.

[0887] Moreover, the deionized water discharging nozzle 7051 isconnected to the deionized water supplying section 7057 through anelectromagnetic valve 7056. Here, reference numeral 7055 represents atube for supplying deionized water.

[0888]FIG. 69 is a block diagram that shows an essential electricalconstruction of the substrate processing apparatus.

[0889] The substrate processing apparatus is provided with a controlsection 7080 having a ROM 7081 in which operation programs required forthe control of the apparatus are stored, a RAM 7082 in which data, etc.,are temporarily stored at the time of the controlling operation and aCPU 7083 for executing logical operations. This control section 7080 isconnected to an electromagnetic valve driving section 7085 for drivingthe above-mentioned electromagnetic valves 7036, 7048, 7056 and 7076, amotor driving section 7086 for driving the above-mentioned motors 7046,7070, and a shifting mechanism driving section 7087 for driving theabove-mentioned nozzle shifting mechanism 7032, brush shifting mechanism7042 and nozzle shifting mechanism 7052, through an interface 7084.

[0890] Next, an explanation will be given of a processing operation forremoving the reaction products from the substrate W by using theabove-mentioned substrate processing apparatus in accordance with thefirst preferred embodiment. FIG. 70 is a flow chart that shows aprocessing operation on the substrate W carried out by the substrateprocessing apparatus in accordance with the first preferred embodiment.

[0891] In the case when, with respect to a substrate W on which a thinfilm formed on its surface has been patterned by dry-etching using aresist film as a mask, resulting reaction products generated on itssurface are removed by using the substrate processing apparatus, aremover liquid supplying step is first executed (step S7011).

[0892] In this remover liquid supplying step (step S7011), the substrateW held by the spin chuck 7070 is rotated at a low speed. Then, thenozzle shifting mechanism 7032 in the remover liquid supplying mechanism7030 is driven so that the remover liquid discharging nozzle 7031 isreciprocally shifted between a position facing the rotation center ofthe rotating substrate W held by the spin chuck 7070 and a positionfacing the end edge of the substrate W, while the electromagnetic valve7036 is opened so as to allow the remover liquid discharging nozzle 7031to discharge the remover liquid. Thus, the remover liquid, heated to apredetermined temperature, is supplied from the remover liquid supplyingsection 7037 to the entire surface of the substrate W that rotates whilebeing held on the spin chuck 7070. Most of the reaction productsgenerated on the surface of the substrate W are removed through thisremover liquid supplying step.

[0893] Next, a remover liquid spinning-off step for spinning off ordispersing the remover liquid adhering to the substrate W is executed byrotating the substrate W at a high speed (step S7012). In this removerliquid spinning-off step, the substrate W is rotated by the spin chuck7070 at a rotation speed of not more than 500 rpm, preferably, at arotation speed of 1000 rpm to 4000 rpm.

[0894] In this case, the reason why the remover liquid spinning-off stepis executed continuously after the remover liquid supplying step isexplained as follows: In the case when an organic alkali liquid, etc.,is used as the remover liquid, upon mixture of deionized water with theresidual remover liquid on the substrate W, a phenomenon, referred to as“pH shock”, occurs in which a strong alkali is generated, causingdamages to the metal wiring. Therefore, it is impossible to continuouslyexecute the remover liquid supplying step and the brush cleaning stepusing deionized water, which will be described later, and aftercompletion of the remover liquid supplying step, it is necessary to usea large amount of an intermediate rinse liquid so as to remove theremover liquid from the substrate W beforehand, and then to carry outthe brush cleaning step by supplying deionized water onto the substrateW. For this reason, the intermediate rinse liquid supplying step takes along time, and the application of a large amount of the intermediaterinse liquid causes high costs.

[0895] In the present preferred embodiment, however, since the removerliquid spinning-off step is carried out continuously after the removerliquid supplying step, it is possible to omit the above-mentionedintermediate rinse supplying step. Moreover, even in the case when theintermediate rinse supplying step is carried out, it is possible tocomplete the intermediate rinse supplying step in a short time by usingonly a small amount of the intermediate rinse liquid.

[0896] Upon completion of the remover liquid spinning-off step, thebrush cleaning step is carried out (step S7013). In the brush cleaningstep, the substrate W, held by the spin chuck 7070, is rotated at a lowspeed. Moreover, the electromagnetic valve 7048 is opened so thatdeionized water is discharged from the deionized water dischargingnozzle 7047 to the surface of the rotating substrate W that is held onthe spin chuck 7070. Then, the rotary brush 7041 is allowed to rotate bythe motor 7046 in the brush cleaning mechanism 7040, and the rotarybrush 7041 is reciprocally shifted between a position that allows it tocontact the rotation center of the rotating substrate W held on the spinchuck 7070 and a position that allows it to contact the end edge of thesubstrate W, by the driving operation of the brush shifting mechanism7042. Thus, the rotary brush 7041 washes the entire surface of therotating substrate W held by the spin chuck 7070. The above-mentionedbrush cleaning step makes it possible to quickly remove the reactionproducts remaining on the surface of the substrate W.

[0897] Here, instead of the arrangement in which the lower end of therotary brush 7041 is made in contact with the rotating substrate W heldon the spin chuck 7070, the rotary brush 7041 may be placed at aposition that makes the lower end slightly apart from the surface of thesubstrate W with a fine gap so as to clean the surface of the substrate.With this arrangement, it is possible to clean the surface of thesubstrate W by using deionized water existing between the lower end ofthe rotary brush 7041 and the surface of the substrate W without givingany impact to the surface of the substrate W.

[0898] After the completion of the brush cleaning step, a deionizedwater supplying step is executed (step S7014). In this deionized watersupplying step, the substrate W, held on the spin chuck 7070, is rotatedat a low speed. Then, the deionized water discharging nozzle 7051 isallowed to reciprocally shift between the position facing the rotationcenter of the rotating substrate W held on the spin chuck 7070 and theposition facing the end edge of the substrate W by the driving operationof the nozzle shifting mechanism 7052 in the deionized water supplyingmechanism 7050, while deionized water is discharged from the deionizedwater discharging nozzle 7051 by opening the electromagnetic valve 7056.Thus, deionized water is supplied from the deionized water supplyingsection 7057 to the entire surface of the rotating substrate W held onthe spin chuck 7070. The surface of the substrate W is washed by thisdeionized water supplying step.

[0899] Here, in the above-mentioned remover liquid supplying step (stepS7011), the brush cleaning step (step S7013) and the deionized watersupplying step (step S7014), the electromagnetic valve 7076 is opened sothat deionized water is supplied to the back surface of the rotatingsubstrate held on the spin chuck 7070 by the back surface cleaningnozzle 7074, and therefore, it is possible to prevent the reactionproducts, etc., removed from the surface of the substrate from furtherreaching the back surface side of the substrate W.

[0900] Lastly, a deionized water spinning-off step for spinning off thedeionized water adhering to the substrate W is executed by rotating thesubstrate W at a high speed (step S7015). In this deionized waterspinning-off step, the substrate W is rotated by the spin chuck 7070 ata rotation speed of not less than 500 rpm, preferably, at a rotationspeed of 1000 rpm to 4000 rpm.

[0901] The removing process of the reaction products is completed byfinishing the above-mentioned steps.

[0902] Additionally, in the above-mentioned preferred embodiment,deionized water is supplied to the surface of the substrate W from thedeionized water injection nozzle 7047 in the brush cleaning step, anddeionized water is supplied to the surface of the substrate W from thedeionized water discharging nozzle 7051 in the deionized water supplyingstep. However, another arrangement may be used, in which either thedeionized water injection nozzle 7047 or the deionized water dischargingnozzle 7048 is omitted and deionized water is supplied to the surface ofthe substrate W through the single nozzle.

[0903] Next, an explanation will be given of another preferredembodiment of the processing operation for removing the reactionproducts from the substrate W by using the substrate processingapparatus in accordance with the above-mentioned first preferredembodiment. FIG. 71 is a flow chart that shows another preferredembodiment of the processing operation of the substrate W carried out byusing the substrate processing apparatus in accordance with the firstpreferred embodiment.

[0904] This preferred embodiment is distinct from the preferredembodiment shown in FIG. 70 in that the deionized water supplying step(step S7023) and the deionized water spinning-off step (step S7024) areexecuted between the remover liquid spinning-off step (step S7022) andthe brush cleaning step (step S7025).

[0905] In other words, in this aspect, upon completion of the removerliquid spinning-off step, a deionized water supplying step is executed(step S7023). In this deionized water supplying step, the substrate W,held on the spin chuck 7070, is rotated at a low speed. Then, by thedriving operation of the nozzle shifting mechanism 7052 in the deionizedwater supplying mechanism 7050, the deionized water discharging nozzle7051 is allowed to reciprocally shift between the position facing therotation center of the rotating substrate W held on the spin chuck 7070and the position facing the end edge of the substrate W, while theelectromagnetic valve 7056 is opened to discharge deionized water fromthe deionized water discharging nozzle 7051. Thus, deionized water issupplied from the deionized water supplying section 7057 to the entiresurface of the rotating substrate W held on the spin chuck 7070. Thesurface of the substrate W is washed by this deionized water supplyingstep.

[0906] Then, a deionized water spinning-off process for spinning off thedeionized water adhering to the substrate W is executed (step S7024). Inthis deionized water spinning-off step, the substrate W is rotated bythe spin chuck 7070 at a speed of not less than 500 rpm, preferably, ata rotation speed of 1000 rpm to 4000 rpm.

[0907] This step makes it possible to process the substrate W morecleanly by cleaning the reaction products with deionized water.

[0908] Next, an explanation will be given of a construction of asubstrate processing apparatus in accordance with another preferredembodiment of the present aspect.

[0909]FIG. 72 is a schematic side view of the substrate processingapparatus in accordance with a second preferred embodiment of thepresent invention. Here, FIG. 72, which corresponds to FIG. 68 inaccordance with the first preferred embodiment, is a drawing that showsthe relationship between a deionized water/intermediate rinse liquidsupplying mechanism 7060 and the scattering preventive cup of the spinchuck 7070.

[0910] The substrate processing apparatus related to the first preferredembodiment has the same construction as the first preferred embodimentexcept that, in place of the deionized water supplying mechanism 7050 inthe substrate processing apparatus of the first preferred embodiment, itis provided with the deionized water/intermediate rinse liquid supplyingmechanism 7060 that supplies both deionized water and an intermediaterinse liquid to the substrate W held on the spin chuck 7070. In thefollowing explanation, those members that are the same as the firstpreferred embodiment are indicated by the same reference numerals, andthe description thereof is omitted.

[0911] As illustrated in FIG. 72, the deionized water/intermediate rinseliquid supplying mechanism 7060 is provided with a deionized waterdischarging nozzle 7051 for discharging deionized water to the substrateW and an intermediate rinse liquid discharging nozzle 7061 fordischarging an intermediate rinse liquid to the substrate W. In the samemanner as the first preferred embodiment, these deionized waterdischarging nozzle 7051 and intermediate rinse liquid discharging nozzle7061 are attached to the tip of an arm 7054 that is allowed to rockcentered on a shaft 7053 directed to the vertical direction by thedriving operation of the nozzle shifting mechanism 7052. For thisreason, the deionized water discharging nozzle 7051 is allowed toreciprocally shift between a position facing the rotation center of therotating substrate W held on the spin chuck 7070 and a position facingthe end edge of the substrate W, and the intermediate rinse liquiddischarging nozzle 7061 is allowed to reciprocally shift between aposition facing the vicinity of the rotation center of the rotatingsubstrate W held on the spin chuck 7070 and a position facing the endedge of the substrate W. Here, the nozzle shifting mechanism 7052 alsohas an arrangement for shifting the arm 7054 in the vertical direction.

[0912] Moreover, the deionized water discharging nozzle 7051 isconnected to the deionized water supplying section 7057 through anelectromagnetic valve 7056, and the intermediate rinse liquiddischarging nozzle 7061 is connected to a supplying section 7067 of theintermediate rinse liquid through an electromagnetic valve 7066. Here,reference numerals 7055, 7065 are tubes for supplying deionized waterand the intermediate rinse liquid respectively.

[0913] Here, the intermediate rinse liquid is a liquid for cleaning theremover liquid away from the substrate W, and examples thereof includean organic solvent such as isopropyl alcohol (IPA) or a functional watersuch as ozone water prepared by dissolving ozone in deionized water andhydrogen water prepared by dissolving hydrogen in deionized water.

[0914] An explanation will be given of a processing operation forremoving the reaction products from the substrate W by using thesubstrate processing apparatus of the second preferred embodiment. FIG.73 is a flow chart that shows the processing operation of the substrateW carried out by the substrate processing apparatus of the secondpreferred embodiment.

[0915] In the case when, with respect to a substrate W on which a thinfilm formed on its surface has been patterned by dry-etching using aresist film as a mask, resulting reaction products generated on itssurface are removed by using the substrate processing apparatus of thesecond preferred embodiment, a remover liquid supplying step is firstexecuted (step S7031) in the same manner as the substrate processingapparatus of the first preferred embodiment.

[0916] In this remover liquid supplying step (step S7031), the substrateW held by the spin chuck 7070 is rotated at a low speed. Then, thenozzle shifting mechanism 7032 in the remover liquid supplying mechanism7030 is driven so that the remover liquid discharging nozzle 7031 isreciprocally shifted between a position facing the rotation center ofthe rotating substrate W held by the spin chuck 7070 and a positionfacing the end edge of the substrate W, while the electromagnetic valve7036 is opened so as to allow the remover liquid discharging nozzle 7031to discharge the remover liquid. Thus, the remover liquid, heated to apredetermined temperature, is supplied from the remover liquid supplyingsection 7037 to the entire surface of the substrate W that rotates whilebeing held on the spin chuck 7070. Most of the reaction productsgenerated on the surface of the substrate W are removed through thisremover liquid supplying step.

[0917] Next, a remover liquid spinning-off step for spinning off theremover liquid adhering to the substrate W is executed by rotating thesubstrate W at a high speed (step S7032). In this remover liquidspinning-off step, the substrate W is rotated by the spin chuck 7070 ata rotation speed of not more than 500 rpm, preferably, at a rotationspeed of 1000 rpm to 4000 rpm.

[0918] Upon completion of the remover liquid spinning-off step, anintermediate rinse liquid supplying step is carried out (step S7033). Inthis intermediate rinse supplying step, the substrate W, held by thespin chuck 7070, is rotated at a low speed. Then, the intermediate rinseliquid discharging nozzle 7061 is allowed to reciprocally shift betweena position facing the vicinity of the rotation center of the rotatingsubstrate W held on the spin chuck 7070 and a position facing the endedge of the substrate W by the driving operation of the nozzle shiftingmechanism 7052 in the deionized water/intermediate rinse liquidsupplying mechanism 7060, while the electromagnetic valve 7066 is openedto allow the intermediate rinse liquid discharging nozzle 7061 todischarge the intermediate rinse liquid. Thus, deionized water issupplied from the supplying section 7067 of the intermediate rinseliquid to the entire surface of the rotating substrate W held on thespin chuck 7070. This intermediate rinse liquid supplying process allowsthe residual deionized water on the surface of the substrate W to bereplaced by the intermediate rinse liquid.

[0919] Here, in the second preferred embodiment also, since the removerliquid spinning-off step is carried out succeeding to the remover liquidsupplying step, it is possible to finish the intermediate rinse liquidsupplying step in a short time by using only a small amount of theintermediate rinse liquid.

[0920] After the completion of the intermediate rinse liquid supplyingprocess, a brush cleaning step is executed (step S7034). In this brushcleaning step, the substrate W, held on the spin chuck 7070, is rotatedat a low speed. Further, the electromagnetic valve 7048 is opened todischarge deionized water from the deionized water injection nozzle 7047onto the surface of the rotating substrate held on the spin chuck 7070.Then, the rotary brush 7041 is allowed to rotate by the motor 7046 inthe brush cleaning mechanism 7040, and the rotary brush is reciprocallyshifted between a position that allows it to contact the rotation centerof the rotating substrate W held on the spin chuck 7070 and a positionthat allows it to contact the end edge of the substrate W, by thedriving operation of the brush shifting mechanism 7042. Thus, the rotarybrush 7041 washes the entire surface of the rotating substrate W held onthe spin chuck 7070. The above-mentioned brush cleaning step makes itpossible to quickly remove the reaction products remaining on thesurface of the substrate W.

[0921] After the completion of the brush cleaning step, a deionizedwater supplying step is executed (step S7035). In this deionized watersupplying step, the substrate W, held on the spin chuck 7070, is rotatedat a low speed. Then, the deionized water discharging nozzle 7051 isallowed to reciprocally shift between a position facing the rotationcenter of the rotating substrate W held on the spin chuck 7070 and aposition facing the end edge of the substrate W by the driving operationof the nozzle shifting mechanism 7052 in the deionizedwater/intermediate rinse liquid supplying mechanism 7060, whiledeionized water is discharged from the deionized water dischargingnozzle 7051 by opening the electromagnetic valve 7056. Thus, deionizedwater is supplied from the deionized water supplying section 7057 to theentire surface of the rotating substrate W held on the spin chuck 7070.Consequently, this deionized water supplying step makes it possible toclean the substrate W.

[0922] Lastly, a deionized water spinning-off step for spinning off thedeionized water adhering to the substrate W is executed by rotating thesubstrate W at a high speed (step S7036). In this deionized waterspinning-off step, the substrate W is rotated by the spin chuck 7070 ata rotation speed of not less than 500 rpm, preferably, at a rotationspeed of 1000 rpm to 4000 rpm.

[0923] The removing process of the reaction products is completed byfinishing the above-mentioned steps.

[0924] Additionally, in the above-mentioned second preferred embodimentalso, deionized water is supplied to the surface of the substrate W fromthe deionized water injection nozzle 7047 in the brush cleaning step,and deionized water is supplied to the surface of the substrate W fromthe deionized water discharging nozzle 7051 in the deionized watersupplying step. However, another arrangement may be used, in whicheither the deionized water injection nozzle 7047 or the deionized waterdischarging nozzle 7048 is omitted and deionized water is supplied tothe surface of the substrate W through the single nozzle.

[0925] Next, an explanation will be given of another preferredembodiment of the processing operation for removing the reactionproducts from the substrate W by using the substrate processingapparatus in accordance with the above-mentioned second preferredembodiment. FIG. 74 is a flow chart that shows another preferredembodiment of the processing operation of the substrate W carried out byusing the substrate processing apparatus in accordance with the secondpreferred embodiment.

[0926] This aspect is distinct from the aspect shown in FIG. 73 in thatthe deionized water supplying step (step S7044) and the deionized waterspinning-off step (step S7045) are executed between the remover liquidsupplying step (step S7043) and the brush cleaning step (step S7046).

[0927] In other words, in this aspect, upon completion of the removerliquid supplying step, a deionized water supplying step is executed(step S7044). In this deionized water supplying step, the substrate W,held on the spin chuck 7070, is rotated at a low speed. Then, by thedriving operation of the nozzle shifting mechanism 7052 in the deionizedwater/intermediate rinse liquid supplying mechanism 7060, the deionizedwater discharging nozzle 7051 is allowed to reciprocally shift betweenthe position facing the rotation center of the rotating substrate W heldon the spin chuck 7070 and the position facing the end edge of thesubstrate W, while the electromagnetic valve 7056 is opened to dischargedeionized water from the deionized water discharging nozzle 7051. Thus,deionized water is supplied from the deionized water supplying section7057 to the entire surface of the rotating substrate W held on the spinchuck 7070. The surface of the substrate W is washed by this deionizedwater supplying step.

[0928] Then, a deionized water spinning-off process for spinning off thedeionized water adhering to the substrate W is executed (step S7045). Inthis deionized water spinning-off step, the substrate W is rotated bythe spin chuck 7070 at a speed of not less than 500 rpm, preferably, ata rotation speed of 1000 rpm to 4000 rpm.

[0929] This step makes it possible to process the substrate W morecleanly by cleaning the reaction products with deionized water.

[0930] Additionally, in both of the above-mentioned preferredembodiments, the remover liquid spinning-off step for removing theresidual remover liquid on the substrate W is executed succeeding to theremover liquid supplying process. However, in the case when a removerliquid that does not cause any pH shock is used, the remover liquidspinning-off process may be omitted.

[0931] (H. Preferred Embodiments According to Eighth Aspect of thePresent Invention)

[0932] <1. Preferred Embodiment of Substrate Processing Apparatus>

[0933]FIG. 75 shows a substrate processing apparatus 8001.

[0934] As illustrated in FIG. 75, the substrate processing apparatus8001 is provided with a doughnut-shaped cup 8003 which has a continuousring shaped wall surface having a virtually U-letter shape in itscross-section, and also has an opening in the center portion thereof,when viewed from above, a holding rotary means 8005 that is formed in amanner so as to stick out through the opening of the cup 8003 in thevertical direction as shown in FIG. 75 and that rotates while holding asubstrate W, a remover liquid supplying means 8007 for supplying aremover liquid to the substrate W held by the holding rotary means 8005and a rinse liquid supplying means 8009 for also supplying a rinseliquid to the substrate W held by the holding rotary means 8005.

[0935] The cup 8003 has a plurality of discharging outlets 8004 on thebottom thereof. Thus, an excessive portion of the liquid supplied to thesubstrate W drops along the inner wall of the cup 8003 to reach thedischarging outlets 8004, and is discharged out of the apparatus throughthe discharging outlets 8004.

[0936] The holding rotary means 8005 is provided with a spin motor 8013which is secured to an apparatus frame, not shown, and has a drivingaxis placed in the vertical direction, a spin shaft 8014 that is securedto the driving shaft of the spin motor 8013 and a vacuum chuck 8015serving as a substrate holding member placed on the top of the spinshaft 8014.

[0937] The vacuum chuck 8015 has a suction surface for sucking thesubstrate on its upper surface and a suction hole, not shown, formed inthe suction surface. Thus, it holds the substrate W virtually in thehorizontal direction by applying air suction trough the suction hole.

[0938] In this arrangement, the holding rotary means 8005 holds thesubstrate W placed on the vacuum chuck 8015 through suction applied bythe vacuum chuck 8015, and rotates the substrate W, centered on a shaft8071, by driving the spin motor 8013.

[0939] The remover liquid supplying means 8007 is provided with a firstrotary motor 8017 which is secured to the apparatus frame, not shown,and has a driving shaft placed in the vertical direction, a first rotaryshaft 8019 secured to the driving shaft of the first rotary motor 8017,a first arm 8021 connected to the top of the first rotary shaft 8019 anda remover liquid nozzle 8011 that is attached to the tip of the firstarm 8021.

[0940] This first arm 8021 is allowed to pivot centered on a shaft 8073as indicated by arrow 8079 so that the remover liquid nozzle 8011 isshifted between a discharging position above the rotation center of thesubstrate W and a stand-by position that is located outside the cup 8003when viewed from above.

[0941] Moreover, a remover liquid source 8024 is connected to theremover liquid nozzle 8011 through a remover liquid valve 8023. Theremover liquid source 8024 sends a pressurized remover liquid that hasbeen temperature-adjusted toward the remover liquid nozzle 8011. Thus,the opening and closing operations of the removing valve 8023 make itpossible to execute and stop the discharging of the remover liquid fromthe remover liquid nozzle 8011.

[0942] Here, a dispersing nozzle 8016 which will be described later isapplied to the remover liquid nozzle 8011.

[0943] The rinse liquid supplying means 8009 is provided with a secondrotary motor 8031 which is secured to the apparatus frame, not shown,and has a driving shaft placed in the vertical direction, a secondrotary shaft 8033 secured to the driving shaft of the second rotarymotor 8031, a second arm 8035 connected to the top of the second rotaryshaft 8033 and a rinse liquid nozzle 8037 that is attached to the tip ofthe second arm 8035.

[0944] This second arm 8035 is allowed to pivot centered on a shaft 8075as indicated by arrow 8077 so that the rinse liquid nozzle 8037 isshifted between a discharging position above the rotation center of thesubstrate W and a stand-by position that is located outside the cup 8003when viewed from above.

[0945] Moreover, a solvent source 8026 is connected to the rinse liquidnozzle 8037 through a solvent valve 8025, and a deionized water source8028 is also connected thereto through a deionized water valve 8027. Thesolvent source 8026 sends a pressurized organic solvent (in this case,isopropyl alcohol) as the intermediate rinse liquid toward the rinseliquid nozzle 8037. Thus, the opening and closing operations of thesolvent nozzle 8025 make it possible to execute and stop the dischargingof the organic solvent from the rinse liquid nozzle 8037.

[0946] Moreover, the deionized water source 8028 sends pressurizeddeionized water toward the rinse liquid nozzle 8037 as the final rinseliquid. The opening and closing operations of the deionized water nozzle8028 makes it possible to execute and stop the discharging of thedeionized water from the rinse liquid nozzle 8037. This arrangementmakes it possible to selectively discharge the organic solvent anddeionized water from the rinse liquid nozzle 8037.

[0947] Here, the dispersing nozzle 8016 which will be described later isapplied to the rinse liquid nozzle 8037.

[0948] <2. Dispersing Nozzle>

[0949] The dispersing nozzle 8016, which will be described below, isapplied to the remover liquid nozzle 8011 and the rinse liquid nozzle8037.

[0950]FIGS. 76A and 76B are a side view and a top view that respectivelyexplain the dispersing nozzle 8016. Here, FIG. 76B is a cross-sectionalview taken along line F76 b-F76 b of FIG. 76A (a cross-sectional view ona plane including the surface of the substrate W).

[0951] As indicated by arrow 8080 in FIG. 76A, the dispersing nozzle8016 discharges the process liquid 8081 with its progressing directiondirected downward (in this case, downward in the vertical directiontoward the rotation center C of the substrate). Moreover, the liquiddischarging operation is executed in such a manner that the processliquid is dispersed downward with an angle θ1 on its side view as shownin FIG. 76A. Here, the dispersing nozzle 8016 discharges a spreadingcurrent of the process liquid 8081 in a manner so as to form a coneshape with an elliptical bottom surface (referred to as elliptical coneshape). In this case, the process liquid 8081 is also present inside theelliptical cone shape in such a manner that the process liquid 8081 isalso supplied into a portion surrounded by an outline 8078 as shown inFIG. 76B.

[0952] In the case when the process liquid is supplied to the substrateby using the dispersing nozzle 8016 of this type, the dischargingpositions of the remover liquid nozzle 8011 and the rinse liquid nozzle8037 are adjusted and the distance between the substrate and thedispersing nozzle 8016 is adjusted by taking the angle θ1 intoconsideration. Thus, the process liquid is supplied to the substrate asdescribed below:

[0953] In other words, in the cross-section (F76 b-F76 b cross-section)on the plane including the surface of the substrate W, the processliquid 8081 is allowed to spread in a manner indicated by an ellipticaloutline 8078, as shown in FIG. 76B. The major axis 8082 of the outline8078 is set to be longer than the diameter 8084 of the substrate W andthe minor axis 8083 is set to be shorter than the diameter 8084, withthe center of the outline 8078 being virtually coincident with therotation center of the substrate W.

[0954] <3. Preferred Embodiment of Substrate Processing Method>

[0955] An explanation will be given of one preferred embodiment of asubstrate processing method using the substrate processing apparatus8001.

[0956] In FIG. 75, the remover liquid nozzle 8011 and the rinse liquidnozzle 8037 are initially positioned respectively at the stand-bypositions outside the cup 8003. Then, a substrate W is placed on thevacuum chuck 8015 and held thereon by a transporting device locatedoutside of the drawing. Next, the discharging nozzle 8011 is shifted tothe discharging position, and the substrate is rotated by the spinmotor. When the number of revolutions of the substrate has reached apredetermined number of revolutions (150 rpm to 1000 rpm, preferably,150 rpm to 500 rpm), the remover liquid valve 8023 is opened so as toexecute a remover liquid supplying step. In this remover liquidsupplying step, a remover liquid is supplied from the remover liquidnozzle 11 to the substrate W that is rotating at the predeterminednumber of revolutions for a predetermined time. Thus, the function ofthe remover liquid sets the reaction products to a state in which theyare allowed to easily come off.

[0957] After a lapse of a predetermined time, the remover liquid valve8023 is closed, while the remover liquid nozzle 8011 is returned to thestand-by position, and the rinse liquid nozzle 8037 is next shifted fromthe stand-by position to the discharging position. Thus, an intermediaterinse step is started.

[0958] In the intermediate rinse step, the solvent valve 8025 is openedso that an organic solvent is supplied as the intermediate rinse liquidfrom the rinse liquid nozzle 8037 to the substrate W that is rotating ata predetermined number of revolutions.

[0959] Consequently, the remover liquid and contaminants are washed awayfrom the substrate W.

[0960] After a lapse of a predetermined time, the solvent valve 8025 isclosed, and the sequence proceeds to a final rinse step.

[0961] In the final rinse step, the deionized water valve 8027 is openedso that deionized water is supplied as the final rinse liquid from therinse liquid nozzle 8037 to the substrate W that is rotating at apredetermined number of revolutions.

[0962] Thus, the organic solvent and contaminants are washed away fromthe substrate W.

[0963] After a lapse of a predetermined time, the deionized water valve8027 is closed.

[0964] Thereafter, the substrate W is rotated at a high speed so that adrying step for drying the substrate W is executed, thereby completingthe sequence of processes.

[0965] As described above, since the dispersing nozzle 8016 is appliedto the removing nozzle 8011, the remover liquid is supplied to theportion surrounded by the outline 8078 of FIG. 76B on the substrate W.In this manner, the remover liquid is allowed to hit a comparativelywide range on the surface of the substrate W. Moreover, since thesubstrate W is rotating at the predetermined number of revolutions, afresh remover liquid is allowed to uniformly hit the substrate W. Sincethis liquid arrival portion being hit by the remover liquid is suppliedwith the remover liquid that has always been adjusted to a predeterminedtemperature and less susceptible to variations in the componentcomposition, it is possible to ensure the in-plane uniformity in theprocess.

[0966] Moreover, both of the intermediate rinse liquid and the finalrinse liquid are supplied through the dispersing nozzle in the samemanner as the remover liquid. For this reason, since a fresh rinseliquid is uniformly supplied to the substrate W, it becomes possible tomore positively ensure the in-plane uniformity in the process.

[0967] Here, in the above-mentioned aspect, the minor axis 8083 of theoutline 8078 is set to be shorter than the diameter 8084 of thesubstrate W. However, the minor axis 8083 may be set to be longer thanthe diameter 8084 of the substrate W. Moreover, the lengths of the majoraxis 8082 and the minor axis 8083 may be made coincident with eachother. In other words, the outline 8078 may include a circle.

[0968] <4. Another Preferred Embodiment of Substrate ProcessingApparatus>

[0969] In the substrate processing apparatus 1, the dispersing nozzle8016 is placed as shown in FIGS. 76A and 76B. However, this may beplaced as shown in FIGS. 77A and 77B.

[0970] As indicated by arrow 8080 a in FIG. 77A, a dispersing nozzle8016 a discharges a process liquid 8081 a with its progressing directiondirected downward (in this case, downward in the vertical direction).Moreover, the liquid discharging operation is executed in such a mannerthat the process liquid 8081 a is dispersed downward with an angle θ2 onits side view. Here, the dispersing nozzle 8016 a discharges the processliquid 8081 a in a manner so as to form a cone shape with an ellipticalbottom surface (referred to as elliptical cone shape), and in this case,the process liquid 8081 a is also present inside the elliptical coneshape in such a manner that the process liquid 8081 a is also suppliedinto a portion surrounded by an outline 8078 a as shown in FIG. 77B.

[0971] In the case when the process liquid is supplied to the substrateby applying the dispersing nozzle 8016 a of this type to the removerliquid nozzle 8011 or the rinse liquid nozzle 8037 of the substrateprocessing apparatus 8001, the discharging position of the removerliquid nozzle 8011 or the rinse liquid nozzle 8037 is adjusted and thedistance between the substrate and the dispersing nozzle 8016 a isadjusted by taking the angle θ2 into consideration. Thus, the processliquid is supplied to the substrate as described below:

[0972] In other words, in the cross-section (F77 b-F77 b cross-section)on the plane including the surface of the substrate W, the processliquid 8081 a is allowed to spread in a manner indicated by anelliptical outline 8078 a, as shown in FIG. 77B. Here, the outline 8078a includes the rotation center C of the substrate and at least one pointon the circumference of the rotation circle P that is formed by the endedge of the rotating substrate. Thus, the process liquid is allowed tohit a comparatively wide range of the surface of the substrate W.Moreover, since the substrate W is rotating at the predetermined numberof revolutions, a fresh remover liquid is allowed to uniformly hit thesubstrate W. Since this liquid arrival portion being hit by the removerliquid is supplied with the remover liquid that has always been adjustedto a predetermined temperature and less susceptible to variations in thecomponent composition, it is possible to ensure the in-plane uniformityin the process.

[0973] In the above-mentioned respective aspects, the process liquid isdispersed in an elliptical cone shape. However, the minor axis 8083 maybe further shortened so as to disperse the process liquid in the form ofa straight line extending in the extending direction of the major axis.

[0974] Moreover, in the above-mentioned respective aspects, thedischarging direction of the process liquid is set perpendicular to thesurface of the substrate W, however, this may be tilted with an angleother than the vertical direction.

[0975] Furthermore, in the above-mentioned respective aspects, thedispersion nozzle 8016 is applied to both of the remover liquid nozzle8011 and the rinse liquid nozzle 8037. This may be applied to either ofthem, and even in this case, it is possible to ensure the in-planeuniformity in the process of the substrate.

[0976] Moreover, upon contact between the remover liquid and deionizedwater, a strong alkali is generated, resulting in a phenomenon referredto as “pH shock” that causes corrosion on the metal film, etc. For thisreason, in the above-mentioned substrate processing method, theintermediate rinse step is prepared. However, in the case of thesubstrate in which the “pH shock” is ignorable, the intermediate rinsestep may be omitted. In this case, of course, the solvent source 8026and the solvent valve 8025 may be omitted from the substrate processingapparatus 8001.

[0977] Furthermore, in the substrate processing in the above-mentionedaspects, the substrate treatment deals with a substrate having a surfaceon which polymers are formed through dry-etching. The present substratetreatment is more effectively applied to a substrate that has beenfurther subjected to ashing after the dry-etching.

[0978] (I. Preferred Embodiments According to Ninth Aspect of thePresent Invention)

[0979] <1. First Preferred Embodiment of Substrate Processing Apparatus>

[0980] The following description will discuss a first preferredembodiment of a substrate processing apparatus of the present invention.

[0981]FIGS. 78 and 79 are drawings that show a construction of asubstrate processing apparatus 9001. Here, FIG. 78 is a cross-sectionalview taken along line F78-F78 of FIG. 79, and for convenience ofexplanation, hatching is partially omitted from some portions.

[0982] As illustrated in FIG. 78, the substrate processing apparatus9001 is provided with a cup 9003 which has a virtually U-letter shape inits cross-section, and also has a virtually ring shape with an openingin the center portion thereof as shown in FIG. 78, when viewed fromabove, a holding rotary means 9005 that is formed in a manner so as tostick out through the opening of the cup 9003 in the vertical directionas shown in FIG. 1 and that rotates while holding a substrate W, aremover liquid nozzle 9007 for supplying a remover liquid to thesubstrate W held by the holding rotary means 9005 and a deionized waternozzle 9009 for also supplying deionized water to the substrate W heldby the holding rotary means 9005. Moreover, the substrate processingapparatus 9001 is also provided with a back surface cleaning nozzle 9011for supplying deionized water to the back surface of the substrate Wheld on the holding rotary means 9005.

[0983] Here, the remover liquid nozzle 9007 corresponds to a removerliquid supplying means in the present invention, and the deionized watersupplying nozzle 9009 corresponds to a deionized water supplying meansin the present invention.

[0984] The cup 9003 has a plurality of discharging outlets 9004 on thebottom thereof. Thus, an excessive portion of the liquid supplied to thesubstrate W drops along the inner wall of the cup 9003 to reach thedischarging outlets 9004, and is discharged out of the apparatus throughthe discharging outlets 9004.

[0985] The holding rotary means 9005 is provided with a spin motor 9013which is secured to an apparatus frame, not shown, and has a drivingshaft placed in the vertical direction, a spin shaft 9014 that issecured to the driving shaft of the spin motor 9013 and a vacuum chuck9015 serving as a substrate holding member placed on the top of the spinshaft 9014.

[0986] The vacuum chuck 9015 has a suction surface for applying airsuction to a substrate on its upper surface, and the suction surface hasan area that is smaller than the area of the substrate W. In the presentaspect, the vacuum chuck is a virtually column shaped member with thesuction surface on its top having a round shape.

[0987] The vacuum chuck 9015 has a suction hole, not shown, formed inthe suction surface that is the upper surface thereof, and air is suckedthrough the suction hole. Thus, the substrate W, placed on the vacuumchuck 15, is held by air suction applied through the suction hole. Inthis manner, the vacuum chuck 15 holds the substrate W by contactingonly the back surface of the substrate W.

[0988] In this arrangement, the holding rotary means 9005 holds thesubstrate W placed on the vacuum chuck 9015 through suction applied bythe vacuum chuck 9015, and rotates the substrate W held on the vacuumchuck 9015 centered on a shaft 9071 by driving the spin motor 9013.

[0989] The remover liquid supplying nozzle 9007 is provided with a firstrotary motor 9017 which is secured to the apparatus frame, not shown,and has a driving shaft placed in the vertical direction, a first rotaryshaft 9019 secured to the driving shaft of the first rotary motor 9017and a first arm 9021 connected to the top of the first rotary shaft9019.

[0990] A remover liquid nozzle main body 9023 is attached to the tip ofthe first arm 9021.

[0991] The remover liquid nozzle main body 9023 is provided with a firstpassage hole 9029 having its axis line direction directed toward the topmajor surface of the substrate W, and a first tube 9027 is connected tothe first passage hole 9029. Moreover, a first vibrator 9025 is placedinside the first passage hole 9029 at a position contacting the removerliquid passing through the first passage hole 9029.

[0992] The first passage hole 9029 is designed so that, when the firstarm 9021 pivots, centered on the shaft 9073 as indicated by arrow 9079,the arrival point of a remover liquid 9081 discharged through the firstpassage hole 9029 on the substrate W is allowed to shift over thesubstrate W along a circular arc as indicated by arrow 9085, passingthrough the rotation center C of the substrate W, as shown in FIG. 79.

[0993] Here, the remover liquid nozzle 9007 discharges the removerliquid in a direction crossing the plane containing the surface of thesubstrate W. In other words, the angle made by the direction of theremover liquid discharged from the remover liquid nozzle 9007 withrespect to the substrate surface is set in the range from greater than 0degree to not more than 90 degrees. In other words, the remover liquidnozzle 9007 discharges the remover liquid in a direction perpendicularto the substrate W or diagonally from above. Preferably, the angle madeby the direction of the remover liquid to be discharged with respect tothe surface of the substrate is set to not less than 30 degrees to notmore than 60 degrees, more preferably, at 45 degrees.

[0994] The first tube 9027 supplies a remover liquid to the firstpassage hole 9029.

[0995] The first vibrator 9025 is allowed to vibrate by an electricsignal from an oscillator 9067, which will be described later, so as toapply ultrasonic waves to the remover liquid passing through the firstpassage hole 9029.

[0996] In the remover liquid nozzle 9007 arranged as described above,the first rotary motor 9017 rotates the first rotary shaft 9019 so thatthe first arm 9021 is allowed to pivot centered on the shaft 9073. Thus,as illustrated in FIG. 79, the arrival point of a remover liquid 9081discharged from the remover liquid nozzle 9007 with respect to thesubstrate W is allowed to shift over the substrate W along a circulararc as indicated by arrow 9085, passing through the rotation center C ofthe substrate W. Thus, the remover liquid to which ultrasonic waves areapplied is supplied to the substrate W.

[0997] The deionized water nozzle 9009 is provided with a second rotarymotor 9031 which is secured to the apparatus frame, not shown, and has adriving shaft placed in the vertical direction, a second rotary shaft9033 secured to the driving shaft of the second rotary motor 9031 and asecond arm 9035 that is connected to the top of the second rotary shaft9033.

[0998] A deionized water nozzle main body 9037 is attached to the tip ofthe second arm 9035.

[0999] The deionized water nozzle main body 9037 is provided with asecond passage hole 9043 having its axis line direction directed towardthe top major surface of the substrate W, and a second tube 9041 isconnected to the second passage hole 9043. Moreover, a second vibrator9039 is placed inside the second passage hole 9043 at a positioncontacting deionized water passing through the second passage hole 9043.

[1000] The second passage hole 9043 is designed so that, when the secondarm 9035 pivots, centered on the shaft 9075 as indicated by arrow 9077,the arrival point of deionized water 9083 discharged through the secondpassage hole 9043 on the substrate W is allowed to shift over thesubstrate W along a circular arc as indicated by arrow 9087, passingthrough the rotation center C of the substrate W, as shown in FIG. 79.

[1001] Here, the deionized water nozzle 9009 discharges deionized waterin a direction crossing the plane containing the surface of thesubstrate W. In other words, the angle made by the direction of thedeionized water discharged from the deionized water nozzle 9009 withrespect to the substrate surface is set in the range from greater than 0degree to not more than 90 degrees. In other words, the deionized waternozzle 9007 discharges deionized water in a direction perpendicular tothe substrate W or diagonally from above. Preferably, the angle made bythe direction of the deionized water to be discharged with respect tothe surface of the substrate is set to not less than 30 degrees to notmore than 60 degrees, more preferably, at 45 degrees.

[1002] The second tube 9041 supplies deionized water to the secondpassage hole 9043.

[1003] The second vibrator 9039 is allowed to vibrate by an electricsignal from an oscillator 9067, which will be described later, so as toapply ultrasonic waves to the deionized water passing through the secondpassage hole 9043.

[1004] In the deionized water nozzle 9009 arranged as described above,the second rotary motor 31 rotates the second rotary shaft 9033 so thatthe second arm 9035 is allowed to pivot centered on the shaft 9075.Thus, as illustrated in FIG. 79, the arrival point of deionized water9083 discharged from the deionized water nozzle 9009 with respect to thesubstrate W is allowed to shift over the substrate W along a circulararc as indicated by arrow 9087, passing through the rotation center C ofthe substrate W. Thus the deionized water to which ultrasonic waves areapplied is supplied to the substrate W.

[1005] A back surface cleaning nozzle 9011 is a tube-shaped member thatpenetrates the cup 9003 and extends virtually in the vertical directiontoward the back surface of the substrate W and used for supplyingdeionized water via a back surface cleaning valve 9065, which will bedescribed later. Thus, it is possible to discharge deionized water ontothe back surface of the substrate W.

[1006] Referring to FIG. 80, the following description will discuss aremover liquid supplying system to the remover liquid nozzle 9007 aswell as a deionized water supplying system 9091 to the deionized waternozzle 9009 and the back surface cleaning nozzle 9011.

[1007] The remover liquid supplying system 9089 is provided with aremover liquid pump 9047 for pumping the remover liquid from a removerliquid source 9045 outside the apparatus, a temperature-adjusting device9051 for adjusting the temperature of the remover liquid by heating orcooling the remover liquid pumped out by the remover liquid pump 9047 toa predetermined temperature, a filter 9049 for filtering contaminantsfrom the remover liquid that has been temperature-adjusted by thetemperature-adjusting device 9051, and a remover liquid nozzle valve9053 for opening and closing the flowing path of the filtered removerliquid to the remover liquid nozzle 9007.

[1008] This arrangement allows the remover liquid supplying system 9089to supply the remover liquid that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 9051 andpurified by the filter 9049 to the remover liquid nozzle 9007.

[1009] The deionized water supplying system 9091 is provided with adeionized water pump 57 for pumping deionized water from a deionizedwater source 9055 outside the apparatus, a temperature-adjusting device9061 for adjusting the temperature of the deionized water by heating orcooling the deionized water pumped out by the deionized water pump 9057to a predetermined temperature, a filter 9059 for filtering contaminantsfrom the deionized water that has been temperature-adjusted by thetemperature-adjusting device 9061, and a deionized water nozzle 9063 foropening and closing the flowing path of the filtered deionized waterliquid to the deionized water nozzle 9009 as well as a back surfacecleaning valve 9065 for opening and closing the flowing path of thedeionized water filtered by the filter 9059 to the back surface cleaningnozzle.

[1010] This arrangement allows the deionized water supplying system 9091to supply the deionized water that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 9061 andpurified by the filter 9059 to the deionized water nozzle 9009.

[1011] Next, referring to FIG. 80, an explanation will be given of anultrasonic wave applying section 9093.

[1012] The ultrasonic wave applying section 9093 is provided with afirst vibrator 9025 placed inside the remover liquid nozzle 9007 and anoscillator 9067 for vibrating the first vibrator 9025 by transmitting anelectric signal to the first vibrator 9025.

[1013] With this arrangement, the ultrasonic wave applying section 9093applies ultrasonic waves to the remover liquid to be supplied to thesubstrate W from the remover liquid nozzle 9007.

[1014] Moreover, the ultrasonic wave applying section 9093 is alsoprovided with a second vibrator 9039 placed inside the deionized waternozzle 9009, and the second vibrator 9039 is vibrated by an electricsignal transmitted from the oscillator 9067.

[1015] With this arrangement, the ultrasonic wave applying section 9093applies ultrasonic waves to the deionized water to be supplied to thesubstrate W from the deionized water nozzle 9009.

[1016] In this manner, the remover liquid with the ultrasonic wavesapplied thereto or the deionized water with the ultrasonic waves appliedthereto is supplied to the substrate W, and therefore, it is possible tocarry out the removing process of the reaction products more quickly,and consequently to improve the throughput. Here, the throughput can beimproved by only applying ultrasonic waves to either the remover liquidor deionized water. However, by applying ultrasonic waves to both of theremover liquid and deionized water, it is possible to remove thereaction products more quickly and to improve the throughput moreeffectively.

[1017] Next, referring to FIG. 81, an explanation will be given of thehardware construction of the substrate processing apparatus 9001.

[1018] To the control means 9069 are connected the spin motor 9013, thefirst rotary motor 9017, the second rotary motor 9031, the oscillator9067, the remover liquid pump 9047, the deionized water pump 9057, theremover liquid nozzle valve 9007, the deionized water nozzle valve 9063,the back surface cleaning valve 9065, the temperature-adjusting device9051 and the temperature-adjusting device 9061, thus, as will bedescribed in first preferred embodiment and second preferred embodimentof a substrate processing method, the control means 9069 controls thesedevices connected thereto.

[1019] <2. First Preferred Embodiment of a Substrate Processing Method>

[1020]FIG. 82 is a drawing that shows a first preferred embodiment of asubstrate processing method in which the above-mentioned substrateprocessing apparatus 9001 is used. As illustrated in FIG. 82, thesubstrate processing method of the present preferred embodiment includesa remover liquid supplying step s9001, a remover liquid spinning-offstep s9002, a deionized water supplying step s9003, and a deionizedwater spinning-off step s9004. Referring to FIG. 83, the followingdescription will discuss the respective steps.

[1021] (1. Remover Liquid Supplying Step s9001)

[1022] First, the control means 9069 has controlled thetemperature-adjusting devices 9051 and 9061 so that the temperatures ofthe remover liquid and deionized water are set to predeterminedtemperatures before the sequence has reached time t9000.

[1023] Moreover, before the sequence has reached time t9000, the controlmeans 9069 drives the spin motor 9013 to rotate the substrate W so thatat time t9000, the substrate W is being rotated at a predeterminednumber of revolutions.

[1024] Then at time t9000, the control means 9069 rotates the firstrotary motor 9017 so as to allow the remover liquid nozzle 9007 topivot.

[1025] Furthermore, at time t9000, the control means 9069 drives theremover liquid pump 9017 so as to send the remover liquid to the removerliquid nozzle 9007, and also allows the remover liquid nozzle valve 9053to open so as to supply the remover liquid from the remover liquidnozzle 9007 to the substrate W. With these steps, the remover liquid,supplied from the remover liquid nozzle 9007, is supplied onto thesubstrate W in such a manner that the arrival point thereof onto thesubstrate W is shifted on a circular arc that passes through therotation center C of the substrate W, and crosses the end edge of thesubstrate W at at least two different points in the horizontal surfaceincluding the surface of the substrate W, as indicated by arrow 9085 inFIG. 79. In this manner, the remover liquid supplying step s9001 isexecuted.

[1026] Here, at time t9000, the control means 9069 allows the oscillator9067 to transmit an electric signal to the first vibrator 9025 withinthe remover liquid nozzle 9007 so as to oscillate the first vibrator9025. Thus, ultrasonic waves are applied to the remover liquid suppliedfrom the remover liquid nozzle 9007. Consequently, the reaction productsadhering to the substrate W are subjected to ultrasonic vibration, andthus easily separated from the substrate W.

[1027] At time t9001 after a lapse of a predetermined time, the controlmeans 9069 stops the driving operation of the first rotary motor 9017 ina state where the remover liquid nozzle 9007 has retreated from aposition above the cup 9003. Moreover, the control means 9069 closes theremover liquid nozzle valve 9053, and also stops the driving operationof the remover liquid pump 9047 so as to stop the supply of the removerliquid from the remover liquid nozzle 9007. Moreover, at time t9001, thecontrol means 9069 stops the transmission of the electric signal fromthe oscillator 9067 to the first vibrator 9025.

[1028] (2. Remover Liquid Spinning-Off Step s9002)

[1029] Next, at time t9001, the control means 9069 stops the supply ofthe remover liquid to the substrate W, while it successively rotates thespin motor 9013 so as to maintain the rotating state of the substrate W.Thus, a remover liquid spinning-off step s9002 is executed.

[1030] In this remover liquid spinning-off step s9002, the substrate Wis rotated at not less than 500 rpm, more preferably, in the range from1000 rpm to 4000 rpm to spin off or disperse the remover liquid from thesubstrate W.

[1031] Moreover, the time during which the rotation is maintained is setto not less than 1 second, preferably, in the range of 2 to 5 seconds.

[1032] In this manner, the rotating state of the substrate is maintainedwith the supply of the remover liquid being stopped with respect to thesubstrate W, the remover liquid on the substrate W is spun off from thesubstrate W by a centrifugal force.

[1033] Furthermore, since the substrate is rotated while beingmaintained in the horizontal state, the remover liquid is spun off fromthe substrate W uniformly. Thus, it is possible to maintain the in-planeuniformity of the substrate W.

[1034] Since the vacuum chuck 9015 is kept in contact with only the backsurface of the substrate W, there are no parts contacting the edge ofthe substrate W. Consequently, since there are no parts that intervenewith the progress the remover liquid that is spun off in the horizontaldirection toward the outside of the substrate W from the top majorsurface of the substrate W, the time required for the remover liquid tobe spun off from the substrate is shortened. Thus, it is possible toimprove the throughput.

[1035] Moreover, since the holding rotary means 9005 only needs to holda single sheet of the substrate W, it is possible to easily increase thenumber of revolutions of the substrate W. For this reason, the timerequired for the remover liquid to be spun off from the substrate isshortened. Thus, it is possible to improve the throughput.

[1036] (3. Deionized Water Supplying Step s9003)

[1037] Next, at time t9002, the control means 9069 rotates the secondrotary motor 9032 so as to allow the deionized water nozzle 9009 topivot.

[1038] At time t9002 also, the control means 9069 drives the deionizedwater pump 9057 so as to send deionized water to the deionized waternozzle 9009, and also allows the deionized water nozzle valve 9063 toopen so as to supply the deionized water from the deionized water nozzle9009 to the substrate W. With these steps, the deionized water, suppliedfrom the deionized water nozzle 9009, is supplied onto the substrate Win such a manner that the arrival point thereof onto the substrate W isshifted on a circular arc that passes through the rotation center C ofthe substrate W, and crosses the end edge of the substrate W at at leasttwo different points in the horizontal surface including the surface ofthe substrate W as indicated by arrow 9087 in FIG. 79. In this manner,the deionized water supplying step s9003 is executed.

[1039] Here, at time t9002, the control means 9069 allows the oscillator67 to transmit an electric signal to the second vibrator 9039 within thedeionized water nozzle 9009 so as to oscillate the second vibrator 9039.Thus, ultrasonic waves are applied to the deionized water supplied fromthe deionized water nozzle 9009. Consequently, the reaction productsadhering to the substrate W are subjected to ultrasonic vibration, andthus easily separated from the substrate W.

[1040] Moreover, at time t9002, the control means 9069 allows the backsurface cleaning valve 9065 to open so as to supply deionized water tothe back surface of the substrate W from the back surface cleaningnozzle 9011, thereby also cleaning the back surface of the substrate W.

[1041] At time t9003 after a lapse of a predetermined time, the controlmeans 9069 stops the driving operation of the second rotary motor 9031in a state where the deionized water nozzle 9009 has retreated from aposition above the cup 3. Moreover, the control means 9069 closes thedeionized water nozzle valve 9063, and also stops the driving operationof the deionized water pump 9057 so as to stop the supply of thedeionized water from the deionized water nozzle 9009. Moreover, at timet9003, the control means 9069 stops the transmission of the electricsignal from the oscillator 9067 to the second vibrator 9039.

[1042] (4. Deionized Water Spinning-Off Step s9004)

[1043] At time t9003, the control means 9069 stops the supply of thedeionized water to the substrate W, while it successively rotates thespin motor 9013 so as to maintain the rotating state of the substrate W.Thus, a deionized water spinning-off step s9004 to spin off or dispersethe deionized water from the substrate W is executed.

[1044] In this manner, the remover liquid and deionized water aresupplied to the substrate W so that the reaction products are removed.

[1045] In accordance with the present preferred embodiment, at theremover liquid spinning-off step s9002, the remover liquid on thesubstrate W is spun off so that the remover liquid remaining on thesubstrate W becomes very little, or no longer exists. Therefore, in thecase when, in this state, the deionized water is supplied to thesubstrate W at the deionized water supplying step s9003, the amount ofthe remover liquid that comes to contact the deionized water becomesvery little or none, and therefore, even in the event of a pH shock,hardly any adverse effect is given to the substrate W, or no pH shockoccurs. Therefore, no intermediate rinse process is required, and thethroughput is consequently improved. Moreover, by omitting theintermediate rinse process, the costs can be reduced, and since anorganic solvent, used for the intermediate rinse process, is no longerrequired, it is possible to improve the safety of the apparatus.

[1046] Moreover, since the remover liquid and deionized water to whichultrasonic waves have been applied are supplied, it is possible toremove the reaction products more quickly.

[1047] Here, in the substrate processing method of the present preferredembodiment, the rotation of the substrate W has not been stopped fromthe start of the remover liquid supplying step s9001 to the completionof the deionized water spinning-off step s9004. However, the rotation ofthe substrate W may be temporarily stopped at any one of the intervalsbetween the remover liquid supplying step s9001 and the remover liquidspinning-off step s9002, between the remover liquid spinning-off steps9002 and the deionized water supplying step s9003 and between thedeionized water supplying step s9003 and the deionized waterspinning-off step s9004.

[1048] The essential thing is to provide at least a step for reducingthe remover liquid on the substrate W by rotating the substrate W evenin a short time, prior to the start of the deionized water supplyingstep s9003.

[1049] Moreover, with respect to the number of revolutions of thesubstrate W, it may be the same or respectively different in the removerliquid supplying step s9001, the remover liquid spinning-off step s9002,the deionized water supplying step s9003 and the deionized waterspinning-off step s9004.

[1050] <3. Second Preferred Embodiment of the Substrate ProcessingMethod>

[1051] Referring to FIG. 84, an explanation will be given of thesubstrate processing method in accordance with a second preferredembodiment.

[1052] The substrate processing method of the second preferredembodiment repeats the substrate processing method of the firstpreferred embodiment twice.

[1053] In other words, the substrate processing method of the presentinvention includes a first remover liquid supplying step s9011, a firstremover liquid spinning-off step s9012, a first deionized watersupplying step s9013, a first deionized water spinning-off processs9014, a second remover liquid supplying step s9021, a second removerliquid spinning-off step s9022, a second deionized water supplying steps9023 and a second deionized water spinning-off step s9024.

[1054] The first remover liquid supplying step s9011 and the secondremover liquid supplying step s9021 are the same as the remover liquidspinning-off step s9002 of the first preferred embodiment.

[1055] Moreover, the first remover liquid spinning-off step s9012 andthe second remover liquid spinning-off step s9022 are the same as theremover liquid spinning-off step s9002 of the first preferredembodiment.

[1056] The first deionized water supplying step s9013 and the seconddeionized water supplying step s9023 are the same as the deionized watersupplying step s9003 of the first preferred embodiment.

[1057] Moreover, the first deionized water spinning-off step s9014 andthe second deionized water spinning-off step s9024 are the same as thedeionized water spinning-off step s9004 of the first preferredembodiment.

[1058] In the substrate processing method of the second preferredembodiment, the first deionized water spinning-off step s9014 is placedbetween the first deionized water supplying step s9013 and the secondremover liquid supplying step s9021. For this reason, the deionizedwater, which has been supplied on the substrate W at the first deionizedwater supplying step s9013, is spun off by the first deionized waterspinning-off process s9014 so that the remaining deionized water on thesubstrate W becomes very little or none. Therefore, in the case when, inthis state, the remover liquid is supplied to the substrate W, theamount of the deionized water that comes to contact the remover liquidbecomes very little or none. Consequently, even in the event of a pHshock, hardly any adverse effect is given to the substrate W, or no pHshock occurs.

[1059] Here, in the present preferred embodiment, the substrateprocessing method of the first preferred embodiment is repeated twice.However, this method may be repeated not less than twice.

[1060] <4. Second Preferred Embodiment of the Substrate ProcessingApparatus>

[1061] Referring to FIGS. 85 and 86, an explanation will be given of asecond preferred embodiment of the substrate processing apparatus of the9^(th) embodiment. Here, FIG. 85 is a cross-sectional view taken alongline F85-F85 of FIG. 86, and, for convenience of explanation, hatchingis omitted from some portions.

[1062] A substrate processing apparatus 9100 of the second preferredembodiment is provided with a solvent nozzle 9002 serving as anintermediate rinse supplying section, in addition to the substrateprocessing apparatus 1 of the first preferred embodiment.

[1063] The substrate processing apparatus 9100 of the second preferredembodiment has many parts that are in common with the substrateprocessing apparatus 9001 of the first preferred embodiment, andtherefore, those parts in common with the substrate processing apparatus9001 are indicated by the same reference numerals, and descriptionthereof is omitted.

[1064] As illustrated in FIG. 85, the substrate processing apparatus9100 has the solvent nozzle 9002.

[1065] The solvent nozzle 9002 is provided with a third rotary motor9018 which is secured to the apparatus frame, not shown, and has adriving shaft placed in the vertical direction, a third rotary shaft9020 secured to the rotary shaft of the third rotary motor 9018 and athird arm 9022 connected to the top of the third rotary shaft 9020.

[1066] A solvent nozzle main body 9024 is installed on the tip of thethird arm 9022.

[1067] The solvent nozzle main body 9024 is provided with a thirdpassage hole 9030 that directs the axis line direction of an organicsolvent to be discharged toward the top major surface of the substrateW, and a third tube 9028 is connected to the third passage hole 9030.Moreover, a third vibrator 9026 is installed inside the third passagehole 9030 at a position contacting the organic solvent that passesthrough the third passage hole 9030.

[1068] The third passage hole 9030 is designed so that, when the thirdarm 9022 pivots, centered on the shaft 9074, the arrival point of anorganic solvent 9081 discharged through the third passage hole 9030 onthe substrate W is allowed to shift over the substrate W along acircular arc as indicated by arrow 9086, passing through the rotationcenter C of the substrate W, as shown in FIG. 86.

[1069] The solvent nozzle 9002 discharges the organic solvent in adirection crossing the plane containing the surface of the substrate W.In other words, the angle made by the direction of the organic solventdischarged from the solvent nozzle 9002 with respect to the substratesurface is set in the range from greater than 0 degree to not more than90 degrees. In other words, the solvent nozzle 9002 discharges theorganic solvent in a direction perpendicular to the substrate W ordiagonally from above. Preferably, the angle made by the direction ofthe organic solvent to be discharged with respect to the surface of thesubstrate is set to not less than 30 degrees to not more than 60degrees, more preferably, at 45 degrees.

[1070] The third tube 9028 supplies an organic solvent to the thirdpassage hole 9030.

[1071] The third vibrator 9026 is allowed to vibrate by an electricsignal from an oscillator 9067 so as to apply ultrasonic waves to theorganic solvent passing through the third passage hole 9030.

[1072] In the solvent nozzle 9002 arranged as described above, the thirdrotary motor 9018 rotates the third rotary shaft 9020 so that the thirdarm 9022 is allowed to pivot centered on the shaft 9074 as indicated byarrow 9078. Thus, as illustrated in FIG. 86, the arrival point of theorganic solvent 9081 discharged from the solvent nozzle 9002 withrespect to the substrate W is allowed to shift over the substrate Walong a circular arc as indicated by arrow 9086, passing through therotation center C of the substrate W. Thus, the organic solvent to whichultrasonic waves have been applied is supplied to the substrate W.

[1073] A back surface solvent nozzle 9012 is a tube-shaped member thatpenetrates the cup 9003 and extends virtually in the vertical directiontoward the back surface of the substrate W, and used for supplying theorganic solvent via a back surface solvent valve 9066, which will bedescribed later. Thus, it is possible to discharge the organic solventonto the back surface of the substrate W.

[1074]FIG. 87 shows an organic solvent supplying system 9090 forsupplying the organic solvent to the organic solvent nozzle 9002.

[1075] The organic solvent supplying system 9090 is provided with asolvent pump 9048 for pumping the organic solvent from a solvent source9046 outside the apparatus, a temperature-adjusting device 9052 foradjusting the temperature of the organic solvent by heating or coolingthe organic solvent pumped out by the solvent pump 9048 to apredetermined temperature, a filter 9050 for filtering contaminants fromthe organic solvent that has been temperature-adjusted by thetemperature-adjusting device 9052, a solvent nozzle valve 9054 foropening and closing the flowing path of the filtered organic solvent tothe solvent nozzle 9002, and a back surface solvent valve 9066 foropening and closing the flowing path of the organic solvent filtered bythe filter 9050 to the back surface solvent nozzle 9012.

[1076] This arrangement allows the solvent supplying system 9090 tosupply the organic solvent that has been temperature-adjusted to apredetermined temperature by the temperature-adjusting device 9052 andpurified by the filter 9050 to the solvent nozzle 9002.

[1077] Moreover, the ultrasonic wave applying section 9093 is providedwith a third vibrator 9026 placed inside the solvent nozzle 9002, andthe third vibrator 9026 is allowed to vibrate by an electric signaltransmitted from the oscillator 9067.

[1078] With this arrangement, the ultrasonic wave applying section 9093applies ultrasonic waves to the organic solvent to be supplied from thesolvent nozzle 9002.

[1079] In this manner, the organic solvent with the ultrasonic wavesapplied thereto is supplied to the substrate W, and therefore, it ispossible to carry out the removing process of the reaction products morequickly, and consequently to improve the throughput. Here, thethroughput can be improved by only applying ultrasonic waves to any oneof the remover liquid, the organic solvent and deionized water, however,by applying ultrasonic waves to any two or all of the remover liquid,the organic solvent and deionized water, it becomes possible to removethe reaction products more quickly and to improve the throughput moreeffectively.

[1080] Next, referring to FIG. 88, an explanation will be given of thehardware construction of the substrate processing apparatus 9100.

[1081] In the same manner as the control means 9069 in the firstpreferred embodiment, to the control means 9070 are connected the spinmotor 9013, the first rotary motor 9017, the second rotary motor 9031,the oscillator 9067, the remover liquid pump 9047, the deionized waterpump 9057, the remover liquid nozzle valve 9007, the deionized waternozzle valve 9063, the back surface cleaning valve 9065, thetemperature-adjusting device 9051 and the temperature-adjusting device9061.

[1082] Moreover, to the control means 9070 are further connected thethird rotary motor 9018, the solvent pump 9048, the solvent nozzle 9054,the back surface solvent valve 9066 and the temperature-adjusting device9052.

[1083] Thus, as will be described in third and fourth preferredembodiments of a substrate processing method, the control means 9070controls these devices connected thereto.

[1084] <5. Third Preferred Embodiment of the Substrate ProcessingMethod>

[1085] Referring to FIG. 89, an explanation will be given of thesubstrate processing method in accordance with a third preferredembodiment in which the above-mentioned substrate processing apparatus9100 is used.

[1086] The substrate processing method of the present preferredembodiment is provided with: a remover liquid supplying step s9031, aremover liquid spinning-off step s9032, a solvent supplying step s9033serving as an intermediate rinse step, a deionized water supplying steps9034 and a deionized water spinning-off process s9035.

[1087] The substrate processing method of the present preferredembodiment is virtually designed by interpolating the solvent supplyingstep between the remover liquid spinning-off step s9002 and thedeionized water supplying step s9003 in the substrate processing methodof the first preferred embodiment including the remover liquid supplyingstep s9001, the remover liquid spinning-off step s9002, the deionizedwater supplying step s9003 and the deionized water spinning-off processs9004.

[1088] Therefore, the above-mentioned remover liquid supplying steps9031, the remover liquid spinning-off step s9032, the deionized watersupplying step s9034 and the deionized water spinning-off step s9035 arerespectively the same as the remover liquid supplying step s9001, theremover liquid spinning-off step s9002, the deionized water supplyingstep s9003 and the deionized water spinning-off step s9004 in thesubstrate processing method of the first preferred embodiment, andtherefore, the description thereof is omitted.

[1089] Next, an explanation will be given of the solvent supplying steps9033 of the present preferred embodiment. As illustrated in FIG. 90,the solvent supplying step s9033 is carried out after the remover liquidsupplying step s9031 and the remover liquid spinning-off step s9032 havebeen finished. In the remover liquid spinning-off process s9032, thesubstrate is kept rotating with the supply of the remover liquid to thesubstrate W being stopped so that the remover liquid on the substrate Wis spun off from the substrate W by a centrifugal force. Thus, theremover liquid remaining on the substrate W is reduced to a minimum.

[1090] Next, at time t9002, the control means 9070 rotates the thirdrotary motor 9018, thereby allowing the solvent nozzle 9002 to pivot.

[1091] At time t9002 also, the control means 9070 drives the solventpump 9048 so as to send the organic solvent to the solvent nozzle 9002,also drives the temperature-adjusting device 9052 to set the organicsolvent to a predetermined temperature, and then opens the solventnozzle valve 9054 so as to supply the organic solvent from the solventnozzle 9002. With these steps, the organic solvent, supplied from thesolvent nozzle 9002, is supplied onto the substrate W in such a mannerthat the arrival point thereof onto the substrate W is shifted on acircular arc that passes through the rotation center C of the substrateW, and crosses the end edge of the substrate W at least two differentpoints in the horizontal surface including the surface of the substrateW as indicated by arrow 9086 in FIG. 86. In this manner, the solventsupplying step s9033 is executed.

[1092] Here, at time t9002, the control means 9070 allows the oscillator9067 to transmit an electric signal to the third vibrator 9026 withinthe solvent nozzle 9002 so as to vibrate the third vibrator 9026. Thus,ultrasonic waves are applied to the organic solvent supplied from thesolvent nozzle 9002.

[1093] Consequently, the reaction products adhering to the substrate Ware subjected to ultrasonic vibration, and thus easily separated fromthe substrate W.

[1094] Moreover, at time t9002, the control means 9070 allows the backsurface solvent valve 9066 to open so as to supply the organic solventto the back surface of the substrate W from the back surface solventnozzle 9012, thereby also cleaning the remover liquid away from the backsurface of the substrate W.

[1095] As described above, in the solvent supplying step s9033, theremover liquid is completely washed away from the substrate W bysupplying the organic solvent to the substrate W. For this reason, evenwhen deionized water is supplied to the substrate W in the succeedingdeionized water supplying step s9034, the remover liquid contactingdeionized water no longer exists, thereby making it possible to preventthe occurrence of a pH shock. Consequently, it becomes possible toprevent damages to thin films on the substrate W.

[1096] Moreover, in the present preferred embodiment, since the removerliquid has been spun off from the substrate W in the remover liquidspinning-off step s9032, the remover liquid remaining on the substrate Wat this point of time is very little. For this reason, it is possible toshorten the time required for the organic solvent to remove the removerliquid in the solvent supplying process s9033. Thus, it becomes possibleto improve the throughput. In the same manner, since the remover liquidremaining on the substrate W is very little, it is possible to reducethe amount of the organic solvent to be required for the solventsupplying step s9033, and consequently to reduce the costs.

[1097] Here, in the present preferred embodiment, the deionized watersupplying step s9034 is executed immediately after the solvent supplyingstep s9033. However, a solvent spinning-off process for spinning thesolvent on the substrate W off may be placed between the solventsupplying step s9033 and the deionized water supplying step s9034.

[1098] Moreover, in the present preferred embodiment, the rotation ofthe substrate W has not been stopped from the start of the removerliquid supplying step s9031 to the completion of the deionized waterspinning-off step s9035. However, the rotation of the substrate W may betemporarily stopped at any one of the intervals between the removerliquid supplying process s9031 and the remover liquid spinning-off steps9032, between the remover liquid spinning-off step s9032 and thesolvent supplying step s9033, between the solvent supplying step s9033and the deionized water supplying step s9034, and between the deionizedwater supplying step s9034 and the deionized water spinning-off steps9035.

[1099] The essential thing is to provide at least a step for reducingthe remover liquid on the substrate W by rotating the substrate W evenin a short time, prior to the start of the solvent supplying step s9033.Consequently, it is possible to shorten the time required for thesolvent supplying step s9035, to improve the throughput, and also toreduce the costs.

[1100] Moreover, in the present preferred embodiment, the removerliquid, the organic solvent and deionized water to which ultrasonicwaves are applied are supplied so that it is possible to remove thereaction products more quickly.

[1101] Furthermore, in the present preferred embodiment, a sequence ofsteps including the remover liquid supplying step s9031, the removerliquid spinning-off step s9032, the solvent supplying step s9033, thedeionized water supplying step s9034 and the deionized waterspinning-off step s9035 are carried out once. However, this sequence ofsteps may be repeated several times.

[1102] In each of the above-mentioned preferred embodiments, the holdingrotary means rotates the substrate while maintaining it horizontally.However, the holding rotary means may rotate the substrate with itsmajor surface being tilted with respect the horizontal surface, or mayrotate the substrate with its major surface being maintained in thevertical direction.

[1103] In each of the above-mentioned preferred embodiments, the holdingrotary means holds only one substrate. However, the holding rotary meansmay be designed to hold a plurality of substrates.

[1104] Furthermore, in each of the above-mentioned preferredembodiments, the substrate treatment deals with a substrate having asurface on which polymers are formed through dry-etching. However, thepresent substrate treatment is more effectively applied to a substratethat has been further subjected to ashing after the dry-etching.

[1105] The ashing is carried out with a substrate having a resist filmbeing placed in an oxygen plasma, and after the ashing, more polymersare generated. For this reason, in the case when a process for removingpolymers from the substrate that has been subjected to the dry-etchingand ashing, the present invention makes it possible to further improvethe throughput, and to reduce the costs more effectively.

[1106] Moreover, in the case when the substrate is rotated while beinghorizontally maintained, since the liquid is allowed to enter theirregularities of the substrate uniformly, it is possible to carry outthe process desirably.

[1107] Furthermore, the liquids such as the remover liquid and deionizedwater are supplied at least in the rotation center C of the substrate,with the substrate W being rotated, the liquids given to the substrateare evenly supplied to the circumferential portion. In particular, inthe case when the substrate is rotated while being horizontallymaintained, since the liquids are evenly supplied to the entire surfaceof the substrate W, it is possible to carry out a uniform processingoperation.

[1108] Since the vacuum chuck 9015 is allowed to hold the substrate Wwhile contacting only the back surface of the substrate W, the liquidsare evenly supplied to the entire surface of the substrate W, inparticular, even onto the circumferential portion of the surface of thesubstrate W. Thus, it is possible to prevent degradation in the processquality.

[1109] In the same manner, since the vacuum chuck 9015 is allowed tohold the substrate W while contacting only the back surface of thesubstrate W, there are no parts contacting the circumferential portionof the substrate. Therefore, when the liquid is spun off from thesubstrate W, the liquid is smoothly discharged from the substrate W.

[1110] The above-mentioned preferred embodiments have disclosed anarrangement in which polymers, generated at the time of dry-etching, areremoved from the substrate that has been subjected to the dry-etchingprocess. However, the present invention is not intended to be limited bythis arrangement in which, from the substrate having polymers generatedat the time of dry-etching, the polymers are removed.

[1111] For example, as described earlier, the present invention alsoincludes a case in which polymers, generated at the time of plasmaashing are removed from the substrate. Thus, the present inventionincludes cases in which, in various processes not limited to thedry-etching, polymers generated due to resist are removed from thesubstrate.

[1112] Moreover, not limited to the cases in which polymers, generatedby the processes such as the dry-etching and plasma ashing, are removed,the present invention includes a case in which various reaction productsderived from resist are removed from the substrate.

[1113] Furthermore, not limited to the case in which the reactionproducts derived from resist are removed from the substrate, the presentinvention includes a case in which resist itself is removed from thesubstrate.

[1114] For example, the present invention includes the following case:with respect to a substrate to which resist is applied, the resist isexposed in a pattern such as a wiring pattern, the resulting resist isdeveloped, and a lower-layer processing is executed on the lower layerof the resist (for example, etching to a thin film serving as the lowerlayer), the resist film, which has become unnecessary after thecompletion of the lower-layer processing, is removed.

[1115] In this case, simultaneously as the unnecessary resist film isremoved, if there are any reaction products derived from a denaturedresist film, these are also removed; therefore, it is possible toimprove the throughput, and also to cut costs. For example, in theabove-mentioned lower-layer processing, when the thin film serving asthe lower layer is subjected to dry-etching, reaction products are alsogenerated. Therefore, the resist film itself, used for masking the lowerlayer at the time of the dry-etching, and the reaction products derivedfrom the denatured resist film are simultaneously removed.

[1116] Moreover, not limited to the cases in which the reaction productsderived from resist and the resist itself are removed from thesubstrate, the present invention is also applied to a case in which,organic substances that are not derived from resist, for example, finecontaminants derived from the human body, are removed from thesubstrate.

[1117] The deionized water supplying means is installed in the substrateprocessing apparatus in the above-mentioned preferred embodiments.However, this may be replaced by a rinse liquid supplying means. In thiscase, a rinse liquid source is installed in place of the deionized watersource, and a rinse liquid from the rinse liquid source is supplied. Inthis case, the rinse liquid is a liquid that turns into water, if leftat room temperature (approximately, 20 degrees to 28 degrees in Celsius)under a normal pressure (approximately, 1 atmospheric pressure).Examples thereof include ozone water prepared by dissolving ozone indeionized water, hydrogen water prepared by dissolving hydrogen indeionized water and water liquid of carbonic acid prepared by dissolvingcarbon dioxide in deionized water. In particular, in the case when ozonewater is used as the rinse liquid in place of deionized water, it ispossible to more completely remove organic substances, reaction productsderived from the denatured resist and polymers. Therefore, this casemakes it possible to achieve the objective of improving the processquality in the processing for removing organic substances, reactionproducts derived from the denatured resist and polymers from thesubstrate.

[1118] In the substrate processing method in the above-mentionedpreferred embodiments, deionized water is supplied to the substrate inthe deionized water supplying step, and the deionized water is spun offfrom the substrate in the deionized water spinning-off step. However,the deionized water supplying step may be replaced by the rinse liquidsupplying step, and the deionized water spinning-off step may bereplaced by the rinse liquid spinning-off step.

[1119] In this case, the rinse liquid is supplied to the substrate inthe rinse liquid supplying step, and the rinse liquid is spun off fromthe substrate in the rinse liquid spinning-off process.

[1120] Therefore, in the above-mentioned preferred embodiments, therinse liquid supplying step and the rinse liquid spinning-off step maybe carried out succeeding to the remover liquid spinning-off step or theintermediate rinse step.

[1121] Here, in the case when the rinse liquid used in the rinse liquidsupplying step is ozone water, it is possible to more completely removeorganic substances, reaction products derived from the denatured resistand polymers. Therefore, this case makes it possible to achieve theobjective of improving the process quality in the processing forremoving organic substances, reaction products derived from thedenatured resist and polymers from the substrate.

[1122] While the invention has been shown and described in detail, theforegoing description is in all aspects illustrative and notrestrictive. It is therefore understood that numerous othermodifications and variations can be devised without departing from thescope of the invention.

1. An apparatus for removing residuary pollution from a substrate, saidapparatus comprising: a) a spin mechanism for holding and rotating saidsubstrate; and b) a liquid supply mechanism for supplying at least oneliquid onto said substrate being rotated, comprising b-1) a mist supplymechanism for mixing a gas with a processing liquid to generate mist andsupplying said mist onto said substrate being rotated in a removingprocess for removing said residuary pollution from said substrate. 2.The apparatus in accordance with claim 1, wherein said mist supplymechanism comprising a mixing part having a mixing room for mixing gaswith said processing liquid to generate said mist, and a nozzle having atapered channel for receiving said mist from said mixing room andsupplying said mist onto said substrate, said channel having a taperedpart being tapered-off toward a discharge end of said channel.
 3. Theapparatus in accordance with claim 2, wherein said liquid supplymechanism is operable to serially supply onto said substrate with: 1) aremover liquid for removing said residuary pollution from said substratebeing rotated, and 2) a deionized water supplied to said substrate beingrotated, and said processing liquid is said deionized water.
 4. Theapparatus in accordance with claim 2, wherein said liquid supplymechanism is operable to serially supply onto said substrate with: 1)remover liquid for removing said residuary pollution from said substratebeing rotated, and 2) deionized water supplied to said substrate beingrotated, and said processing liquid is said remover liquid.
 5. Theapparatus in accordance with claim 2, wherein said liquid supplymechanism is operable to serially supply onto said substrate with: 1)remover liquid for removing said residuary pollution from said substratebeing rotated, 2) intermediate rinse for removing said remover liquidfrom said substrate being rotated, and 3) a deionized water supplied tosaid substrate being rotated, and said processing liquid is saidintermediate rinse.
 6. The apparatus in accordance with claim 2, whereinsaid nozzle supplies said mist onto said substrate at a directioninclined from a normal direction of a major surface of said substrate.7. The apparatus in accordance with claim 3, wherein said mist supplymechanism further comprising a straight part having an even crosssection for receiving said mist from said tapered channel to dischargesaid mist onto substrate.
 8. The apparatus in accordance with claim 2,wherein said mixing room has a smooth inner wall.
 9. The apparatus inaccordance with claim 2, wherein said mixing part further comprising atube through which said gas is introduced into said mixing room, and aring-shaped space enclosing said tube, through which said processingliquid is introduced into said mixing room.
 10. The apparatus inaccordance with claim 1, wherein said mist supply mechanism comprising:a gas discharge mechanism for discharging said gas into an open space onsaid substrate; and a processing liquid discharge mechanism fordischarging said processing liquid into said gas in said open space togenerate said mist to be applied to said substrate.
 11. The apparatus inaccordance with claim 10, wherein said gas and said processing liquidcollide with each other in said open space to generate said mist. 12.The apparatus in accordance with claim 10, wherein one of said gas andsaid processing liquid is discharged into said free space as a flow, andthe other of said gas and said processing liquid is discharged into saidflow.
 13. The apparatus in accordance with claim 10, wherein said gas isdischarged in a first direction, and said processing liquid isdischarged in a second direction, wherein an angle between said firstand second directions is within zero to 110 degree.
 14. The apparatus inaccordance with claim 1, wherein said mist supply mechanism comprising:a processing liquid discharge mechanism having a first dischargingoutlet for discharging said processing liquid into an open space; and agas discharge mechanism having a second discharging outlet fordischarging said gas into said processing liquid in said open space justafter said processing liquid is discharged from said first dischargingoutlet, to thereby convert said processing liquid into liquid dropsconstituting said mist.
 15. The apparatus in accordance with claim 14,further comprising: c) a controller for controlling said mist supplymechanism, comprising a first control element for starting discharge ofsaid gas, and a second control element for starting discharge of saidprocessing liquid when a first predetermined time is elapsed afterdischarge of said gas is started.
 16. The apparatus in accordance withclaim 15, wherein said controller further comprising a third controlelement for stopping the discharge of said processing liquid, and afourth control element for stopping the discharge of said gas when asecond predetermined time is elapsed after discharge of said processingliquid is stopped.
 17. An apparatus for removing residuary pollutionfrom a substrate, comprising: a) a spin mechanism for holding androtating said substrate; and b) a remover liquid supply unit forsupplying remover liquid onto said substrate being rotated to removesaid residuary pollution from said substrate, c) a deionized watersupply unit for supplying a deionized water onto said substrate beingrotated, and d) at least one ultrasonic oscillator for applyingultrasonic wave to at least one of said remover liquid and saiddeionized water.
 18. The apparatus in accordance with claim 17, whereinsaid residuary pollution is caused in a dry-etching process in which athin film formed on said substrate is removed through a dry-etching stepusing a resist film as a mask.
 19. The apparatus in accordance withclaim 17, wherein origin of said residuary pollution is a resist used inan etching process of a thin film formed on said substrate.
 20. Theapparatus in accordance with claim 17, wherein said residuary pollutionis an organic matter.
 21. The apparatus in accordance with claim 17,wherein said remover liquid supply unit supplies said remover liquidonto said substrate in a direction inclined from a normal direction of amajor surface of said substrate.
 22. The apparatus in accordance withclaim 21, further comprising: e) a driving mechanism for moving saidremover liquid supply unit to scan said substrate with a reach point ofsaid remover liquid on said substrate along a path connecting a rotationcenter of said substrate and a rotation circle defined by an edge ofsaid substrate being rotated.
 23. The apparatus in accordance with claim17, wherein said deionized water supply unit supplies said deionizedwater onto said substrate in a direction inclined from a normaldirection of a major surface of said substrate.
 24. The apparatus inaccordance with claim 17, further comprising: e) a driving mechanism formoving said deionized water supply unit to scanning said substrate witha reach point of said deionized water on said substrate along a pathconnecting a rotation center of said substrate and a rotation circledefined by an edge of said substrate being rotated.
 25. An apparatus forremoving residuary pollution from a substrate, comprising: a) a spinmechanism for holding and rotating said substrate; and b) a removerliquid supply unit for supplying remover liquid onto said substratebeing rotated to remove said residuary pollution from said substrate, c)an intermediate rinse remover liquid supply unit for supplyingintermediate rinse onto said substrate being rotated to remove saidremover liquid from said substrate, d) a deionized water supply unit forsupplying a deionized water onto said substrate being rotated, and e) atleast one ultrasonic oscillator for applying ultrasonic wave to at leastone of said remover liquid, said intermediate rinse and said deionizedwater.
 26. The apparatus in accordance with claim 25, wherein saidintermediate rinse supply unit supplies said intermediate rinse ontosaid substrate in a direction inclined from a normal direction of amajor surface of said substrate.
 27. The apparatus in accordance withclaim 26, further comprising: f) a driving mechanism for moving saidintermediate rinse supply unit to scanning said substrate with anarrival point of said intermediate rinse on said substrate along a pathconnecting a rotation center of said substrate and a rotation circledefined by an edge of said substrate being rotated.
 28. An apparatus forremoving residuary pollution caused in an dry-etching process from asubstrate, said apparatus comprising: a) a spin mechanism for holdingand rotating said substrate; and b) a remover liquid supply unit forsupplying remover liquid onto said substrate being rotated to removesaid residuary pollution from said substrate while scanning saidsubstrate with said remover liquid.
 29. The apparatus in accordance withclaim 28, wherein said remover liquid supply unit comprising b-1) aremover liquid discharging unit for discharging said remover liquid ontosaid substrate being rotated, and b-2) a driving unit for moving saidremover liquid discharging unit to scan said substrate with said removerliquid.
 30. The apparatus in accordance with claim 29, wherein saiddriving unit moves said remover liquid emission unit such that anarrival point of said remover liquid on said substrate is moved along apath connecting a rotation center of said substrate and a rotationcircle defined by an edge of said substrate being rotated.
 31. Theapparatus in accordance with claim 30, wherein said path is an arcconnecting said rotation center of said substrate and said rotationcircle.
 32. The apparatus in accordance with claim 29, wherein atemperature of said remover liquid supplied from said remover liquidsupply unit is controlled.
 33. The apparatus in accordance with claim32, wherein said remover liquid discharging unit comprises a temperaturecontroller for controlling a temperature of said remover liquid, and atransmission mechanism for transmitting said remover liquid whosetemperature is controlled to said substrate.
 34. The apparatus inaccordance with claim 29, further comprising: a ultrasonic wave isapplied to said remover liquid.
 35. The apparatus in accordance withclaim 34, wherein said ultrasonic wave is applied to said remover liquidbefore said remover liquid is applied onto said substrate.
 36. Theapparatus in accordance with claim 35, wherein said remover liquidemission unit comprises an ultrasonic oscillator contacting said removerliquid to apply said ultrasonic wave to said remover liquid.
 37. Anapparatus for removing residuary pollution caused in an dry-etchingprocess from a substrate, said apparatus comprising: a) a spin mechanismfor holding and rotating said substrate; and b) a remover liquid supplymechanism comprising: b-1) a pressure generator for applying pressure toa remover liquid which is effective for removing said chemical residuarypollution to generate a pressured remover liquid, and b-2) a nozzle fordischarging said pressured remover liquid onto said substrate beingrotated, and c) a deionized water supply mechanism for supplyingdeionized water onto said substrate being rotated.
 38. The apparatus inaccordance with claim 37, wherein said pressure generator comprising acylinder having a closed end and defining a room therein, and a pistondriven by a piston driver to move in said cylinder to apply pressure tosaid remover liquid introduced from an inlet into said room and sendsaid pressured remover liquid from an outflow port.
 39. An apparatus forremoving chemical residuary pollution caused in an dry-etching processfrom a substrate, said apparatus comprising: a) a spin mechanism forholding and rotating said substrate; and b) a remover liquid supply unitfor supplying remover liquid onto said substrate being rotated to removesaid chemical residuary pollution from said substrate being rotated, andc) a deionized water supply mechanism comprising: c-1) a pressuredgenerator for applying pressure to deionized water to generate apressured remover liquid, and c-2) a nozzle for discharging saidpressured deionized water onto said substrate being rotated.
 40. Anapparatus for removing chemical residuary pollution caused in andry-etching process from a substrate, said apparatus comprising: a) aspin mechanism for holding and rotating said substrate; and b) a removerliquid supply unit for supplying remover liquid onto said substratebeing rotated to remove said chemical residuary pollution from saidsubstrate being rotated, c) an intermediate rinse supply mechanismcomprising: c-1) a pressured generator for applying pressure tointermediate rinse to generate a pressured intermediate rinse, and c-2)a nozzle for discharging said pressured intermediate rinse onto saidsubstrate being rotated, and d) a deionized water supply mechanism forsupplying said deionized water onto said substrate being rotated.
 41. Anapparatus for removing residuary pollution caused in an dry-etchingprocess from a substrate, said apparatus comprising: a) a remover liquidsupply unit comprising a remover liquid discharging unit for dischargingremover liquid onto said substrate being rotated to remove saidresiduary pollution from said substrate, b) a temperature controller forcontrolling a temperature of said remover liquid, c) a driver for movingsaid remover liquid discharging unit between a processing position fromwhich said remover liquid is discharged onto said substrate, and astand-by position from which said remover liquid is discharged to aposition defined out of said substrate, and d) a controller forcontrolling said driver and said remover liquid discharging unit suchthat said remover liquid discharging unit is located at said stand-byposition and discharges said remover liquid to said position defined outof said substrate, and said remover liquid discharging unit is thenmoved to said processing position and discharges said remover liquidonto said substrate.
 42. The apparatus in accordance with claim 41,further comprising: e) a collection mechanism for collecting saidremover liquid having been discharged from said remover liquiddischarging unit from said stand-by position.
 43. The apparatus inaccordance with claim 42, wherein said controller controls said removerliquid supply unit to intermittently discharge said remover liquidduring said remover liquid discharging unit is located at said stand-byposition.
 44. An apparatus for removing residuary pollution caused in andry-etching process from a substrate, said apparatus comprising: a) aremover liquid supply unit comprising a remover liquid discharging unitfor discharging remover liquid onto said substrate being rotated toremove said residuary pollution from said substrate, b) a temperaturecontroller for controlling a temperature of said remover liquid, c) adriver for moving said remover liquid emission unit between a processingposition from which said remover liquid is discharged onto saidsubstrate, and a stand-by position from which said remover liquid isdischarged to a position defined out of said substrate, and d) acontroller for controlling said remover liquid discharging unit todischarge said remover liquid to said position defined out of saidsubstrate during said remover liquid discharging unit is located at saidstand-by position.
 45. The apparatus in accordance with claim 44,further comprising: e) a collection mechanism for collecting saidremover liquid having been discharged from said remover liquiddischarging unit from said stand-by position.
 46. The apparatus inaccordance with claim 45, wherein said controller controls said removerliquid supply unit to intermittently discharge said remover liquidduring said remover liquid discharging unit is located at said stand-byposition.
 47. An apparatus for removing residuary pollution from asubstrate, comprising: a) a spin mechanism for holding and rotating saidsubstrate; b) a remover liquid supply unit for supplying remover liquidonto said substrate being rotated to remove said residuary pollutionfrom said substrate; c) a brush unit for brushing said substrate; d) adeionized water supply unit for supplying a deionized water onto saidsubstrate being rotated; and d) a controller comprising a first controlprocedure element for controlling said remover liquid supply unit tosupply said remover liquid onto said substrate being rotated, a secondcontrol procedure element for controlling said brush unit to brush saidsubstrate after said remover liquid is supplied onto said substratebeing rotated, a third control procedure element for controlling saiddeionized water supply unit to supply said deionized water onto saidsubstrate being rotated after said substrate is brushed, and a fourthcontrol procedure element for controlling said spin mechanism to rotatesaid substrate to disperse said deionized water from said substrate. 48.The apparatus in accordance with claim 47, wherein said controllerfurther comprises a fifth control procedure element for controlling saidspin mechanism to rotate said substrate to disperse said remover liquidfrom said substrate after said remover liquid is supplied onto saidsubstrate and before said substrate is brushed.
 49. The apparatus inaccordance with claim 48, further comprising e) an intermediate rinsesupply unit for supplying said intermediate rinse onto said substratebeing rotated, wherein said controller further comprises a sixth controlprocedure element for controlling said intermediate rinse supply unit tosupply said intermediate rinse onto said substrate being rotated beforesaid remover liquid is dispersed from said substrate and before saidsubstrate is brushed.
 50. An apparatus for removing residuary pollutionfrom a substrate, comprising: a) a spin mechanism for holding androtating said substrate; and b) a processing liquid supply unitcomprising a nozzle for discharging a spreading current of a processingliquid toward said substrate.
 51. The apparatus in accordance with claim50, wherein said processing liquid is a remover liquid for removing saidresiduary pollution from said substrate.
 52. The apparatus in accordancewith claim 50, wherein said processing liquid is rinse for rinsing aremover liquid having been applied onto said substrate to remove saidresiduary pollution from said substrate.
 53. The apparatus in accordancewith claim 50, wherein a cross section of said spreading current on saidsubstrate is substantially an ellipse including a rotation center ofsaid substrate and at least one point on a rotation circle defined by anedge of said substrate being rotated.
 54. The apparatus in accordancewith claim 50, wherein said nozzle discharges said spreading currentfrom a location above a rotation center of said substrate, and a crosssection of said spreading current on said substrate is substantially anellipse having a major axis longer than a diameter of said substrate.55. An apparatus for removing residuary pollution from a substrate,comprising: a) a spin mechanism for holding and rotating said substrate;b) a remover liquid supply unit for supplying remover liquid onto saidsubstrate being rotated to remove said residuary pollution from saidsubstrate, c) a deionized water supply unit for supplying a deionizedwater onto said substrate being rotated; and d) a controller comprisinga first control procedure element for controlling said remover liquidsupply unit to supply said remover liquid onto said substrate beingrotated, a second control procedure element for controlling said spinmechanism to rotate said substrate to disperse said remover liquid fromsaid substrate, and a third control procedure element for controllingsaid deionized water supply unit to supply said deionized water ontosaid substrate being rotated after said remover liquid is dispersed. 56.The apparatus in accordance with claim 55, further comprising e) anintermediate rinse supply unit for supplying said intermediate rinseonto said substrate being rotated, wherein said controller furthercomprises a fourth control procedure element for controlling saidintermediate rinse supply unit to supply said intermediate rinse ontosaid substrate being rotated before said remover liquid is dispersedfrom said substrate and before said deionized water is supplied.
 57. Theapparatus in accordance with claim 55, wherein said residuary pollutionis caused in a dry-etching process in which a thin film formed on saidsubstrate is removed through a dry-etching step using a resist film as amask.
 58. The apparatus in accordance with claim 57, wherein saidresiduary pollution is a polymer, and said remover liquid is organicalkali liquid orinorganic acid.
 59. The apparatus in accordance withclaim 58, wherein said remover liquid is selected from a groupconsisting of dimethylformamide, dimethyl sulfoxide and hydroxylamine.60. The apparatus in accordance with claim 58, wherein said removerliquid is selected from a group consisting of hydrofluoric acid andphosphoric acid.
 61. The apparatus in accordance with claim 55, whereinsaid residuary pollution is an organic matter.
 62. The apparatus inaccordance with claim 61, wherein said organic matter is a polymer. 63.The apparatus in accordance with claim 61, wherein said remover liquidis one of a first remover liquid including organic amine, a secondremover liquid including ammonium bifluoride, and an inorganic removerliquid.